JP5803076B2 - Polymerizable liquid crystal compound and polymer thereof - Google Patents

Description

  The present invention relates to a liquid crystal compound having a cyclohexene oxide moiety as a polymerizable group, a polymer thereof, and a film having optical anisotropy.

  In recent years, polymerizable liquid crystal compounds have been used for optically anisotropic materials such as polarizing plates and retardation plates. This is because this compound exhibits optical anisotropy in a liquid crystal state, and liquid crystal molecules in this state are fixed by polymerization. Since the optical properties required for the polymer having optical anisotropy vary depending on the purpose, a compound having the properties suitable for the purpose is required. In addition to the optical anisotropy described above, the properties of the compound used for such purposes are also important. The properties necessary for this polymerizable liquid crystal compound (composition) and its polymer are compatibility, solubility, clearing point, coatability, polymerization rate, transparency, melting point, crystallinity, glass transition point, shrinkage, water permeability. Degree, water absorption, mechanical strength, chemical resistance, heat resistance, etc.

  Among the polymerizable liquid crystal compounds, compounds having an acryloyloxy group as a polymerizable group are widely used for such purposes (Patent Documents 1 and 2). These acrylates are highly reactive and the resulting polymer is highly transparent. However, since the polymerization mode is a radical polymerization reaction, it is necessary to carry out the reaction in an inert gas or increase the energy of ultraviolet irradiation. Therefore, improvement in workability by curing in air and further improvement in properties such as heat resistance, shrinkage, adhesion, adhesion, and mechanical strength of the polymer are also required. The polymerizable liquid crystal compound (composition) can be used as an ink to which an organic solvent has been added for the purpose of adjusting coating properties. In order to produce a film having optical anisotropy, a polymerizable liquid crystal compound (composition), a photopolymerization initiator, a surfactant, and the like are dissolved in an organic solvent to prepare an ink having adjusted viscosity, leveling properties, and the like. . This ink is applied to a transparent substrate film subjected to orientation treatment, the solvent is dried, and the polymerizable liquid crystal compound (composition) is oriented. Next, it is polymerized by ultraviolet irradiation or heat to fix the alignment state. The organic solvent used in this step is preferably propylene glycol monoethyl ether acetate (PGMEA) from the viewpoints of environmental load and safety (mutagenicity, toxicity). However, the compounds disclosed in Non-Patent Documents 1 and 2 are not highly soluble in such a solvent to prepare an ink having an appropriate concentration. The claims of Patent Documents 3 to 6 disclose compounds similar to the compound of the present invention, but none of these documents describes the compound of the present invention and its effects specifically.

JP-A-7-17910 JP-A-9-316032 JP 2008-239567 A JP 2008-110948 A JP 2008-239568 A JP 2010-037881 A

Polymer Chemistry, 1993, 31 (9), 2249-60. Polymer, 1994, 35 (3), 622-9.

  The first object of the present invention is to have a liquid crystal phase in a wide temperature range centering on room temperature, exhibit excellent compatibility with other polymerizable liquid crystal compounds, have high solubility in organic solvents, and can be used in the air. It is to provide a polymerizable liquid crystal compound that can be polymerized by heat and light. The second purpose is to provide optical properties having a plurality of excellent properties among transparency, mechanical strength, shrinkage, water permeability, water absorption, melting point, glass transition point, clearing point, chemical resistance, heat resistance and the like. It is to provide a polymer exhibiting anisotropy. The third object is to provide a liquid crystal display element containing a polymer exhibiting this optical anisotropy.

ここに、Ａ^１およびＡ^２は独立して１，４−シクロへキシレン、１，４−フェニレン、ピリジン−２，５−ジイル、ピリミジン−２，５−ジイル、ナフタレン−２，６−ジイル、テトラヒドロナフタレン−２，６−ジイル、１，３−ジオキサン−２，５−ジイルまたはフルオレン−２，７−ジイルであり；
この１，４−フェニレンおよびフルオレン−２，７−ジイルにおいて、任意の水素はフッ素、塩素、シアノ、メチル、エチル、メトキシ、ヒドロキシ、ホルミル、アセトキシ、アセチル、トリフルオロアセチル、ジフルオロメチルまたはトリフルオロメチルで置き換えられてもよく；Ｚ^１は単結合、−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＨ＝ＣＨ−ＣＯＯ−、−ＯＣＯ−ＣＨ＝ＣＨ−、−ＯＣＯ−ＣＨ_２ＣＨ_２−、−ＣＨ_２ＣＨ_２−ＣＯＯ−、−Ｃ≡Ｃ−ＣＯＯ−、−ＯＣＯ−Ｃ≡Ｃ−、−ＣＨ_２Ｏ−、−ＯＣＨ_２−、−ＣＦ_２Ｏ−、−ＯＣＦ_２−、−ＣＯＮＨ−、−ＮＨＣＯ−、−（ＣＨ_２）_４−、−ＣＨ_２ＣＨ_２−、−ＣＦ_２ＣＦ_２−、−ＣＨ＝ＣＨ−、−ＣＦ＝ＣＦ−または−Ｃ≡Ｃ−であり；ｍは０〜５の整数であり；ｍが２以上であるとき、環Ａ^２の任意の２つは同じであってもよく、または異なってもよく、Ｚ^１の任意の２つは同じであってもよく、または異なってもよく；Ｐ^１は式（２−１）で表される重合性基であり；Ｑ^１は炭素数１〜２０のアルキレンであり、このアルキレン中の任意の水素はフッ素で置き換えられてもよく、任意の−ＣＨ_２−は−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられてもよく；Ｐ^２は式（２−１）〜式（２−４）のいずれか１つで表される重合性基、水素、フッ素、塩素、シアノ、トリフルオロメチル、トリフルオロメトキシ、炭素数１〜２０のアルキル、または炭素数１〜２０のアルコキシであり；Ｑ^２は、Ｐ^２が重合性基であるときＱ^１と同じように定義される基であり、Ｐ^２が重合性基でないときは単結合である。

（ここに、Ｒ^aは独立して水素、ハロゲン、または炭素数１〜５のアルキルである。） The polymerizable liquid crystal compound of the present invention is shown in the following item [1].
[1] Polymerizable liquid crystal compound represented by formula (1):

Wherein A ¹ and A ² are independently 1,4-cyclohexylene, 1,4-phenylene, pyridine-2,5-diyl, pyrimidine-2,5-diyl, naphthalene-2,6-diyl, Tetrahydronaphthalene-2,6-diyl, 1,3-dioxane-2,5-diyl or fluorene-2,7-diyl;
In this 1,4-phenylene and fluorene-2,7-diyl, any hydrogen is fluorine, chlorine, cyano, methyl, ethyl, methoxy, hydroxy, formyl, acetoxy, acetyl, trifluoroacetyl, difluoromethyl or trifluoromethyl. Z ¹ is a single bond, —O—, —COO—, —OCO—, —CH═CH—COO—, —OCO—CH═CH—, —OCO—CH ₂ CH ₂ —, —CH ₂ CH ₂ —COO—, —C≡C—COO—, —OCO—C≡C—, —CH ₂ O—, —OCH ₂ —, —CF ₂ O—, —OCF ₂ —, —CONH— , —NHCO—, — (CH ₂ ) ₄ —, —CH ₂ CH ₂ —, —CF ₂ CF ₂ —, —CH═CH—, —CF═CF— or —C≡C—; ~ 5 adjustment In it, when m is 2 or more, any two of ring A ² may be the same or different may be, any two of Z ¹ may be the same or different P ¹ is a polymerizable group represented by the formula (2-1); Q ¹ is an alkylene having 1 to 20 carbon atoms, and any hydrogen in the alkylene may be replaced by fluorine. Well, any —CH ₂ — may be replaced by —O—, —COO—, —OCO—, —CH═CH— or —C≡C—; P ² may be of formula (2-1) to formula The polymerizable group represented by any one of (2-4), hydrogen, fluorine, chlorine, cyano, trifluoromethyl, trifluoromethoxy, alkyl having 1 to 20 carbons, or alkoxy having 1 to 20 carbons by and; Q ² is defined the same as Q ¹ when P ² is a polymerizable group A group, when P ² is not a polymerizable group is a single bond.

(Here, R ^a is independently hydrogen, halogen, or alkyl having 1 to 5 carbon atoms.)

  The polymerizable liquid crystal compound of the present invention has a wide range of liquid crystal phases centered at room temperature, exhibits excellent compatibility with other polymerizable liquid crystal compounds, has high solubility in organic solvents, and polymerizes at room temperature. In particular, it satisfies a plurality of characteristics such as polymerization, polymerization by heat, easy polymerization, chemical stability, and colorlessness. In particular, it is excellent in solubility in a highly safe solvent when used as an ink. Further, the polymer obtained using this polymerizable liquid crystal compound as a raw material has an appropriate optical anisotropy, is difficult to peel off from the support substrate, has sufficient hardness, is colorless and transparent, and has high heat resistance. It satisfies a plurality of characteristics such as excellent weather resistance and low photoelasticity. Therefore, the polymer of the present invention can be used for, for example, a retardation plate, a polarizing element, an antireflection film, a selective reflection film, a brightness enhancement film, and a viewing angle compensation film, which are components of a liquid crystal display element.

First, terms used in the present invention will be described. The meaning of the term “liquid crystalline” is not limited to having a liquid crystal phase. Even if it does not have a liquid crystal phase itself, a characteristic that can be used as a component of a liquid crystal composition when mixed with another liquid crystal compound is also included in the meaning of liquid crystal. The polymerizable liquid crystal compound represented by formula (1) may be referred to as compound (1). Similarly, compounds represented by other formulas may be abbreviated. The term “arbitrary” used in describing chemical formula symbols means “not only the position of an element (or functional group) but also its number can be freely selected”. And for example, the expression “any A may be replaced by B, C, D or E” means that one A may be replaced by any one of B, C and D, and any A May be replaced with two of B, C or D, and any two of A may be replaced with B and C, B and D, or C and D. When any —CH ₂ — may be replaced by —O—, such a replacement that results in the linking group —O—O— is not included. In addition, in the Example, the display data of the electronic balance was shown using g (gram) which is a mass unit. Weight% and parts by weight are data based on such numerical values.

The present invention comprises the above item [1] and the following items [2] to [29].
[2] A ¹ and A ² are independently 1,4-cyclohexylene, 1,4-phenylene, naphthalene-2,6-diyl or fluorene-2,7-diyl, The polymerizable liquid crystal compound according to item [1], wherein any one or two hydrogen atoms in fluorene-2,7-diyl may be replaced with fluorine, methyl or trifluoromethyl.

[3] Z ¹ is a single bond, —COO—, —OCO—, —CH═CH—COO—, —CH ₂ CH ₂ —COO—, —OCO—CH═CH—, —OCO—CH ₂ CH ₂ —. The polymerizable liquid crystal compound according to the item [1] or [2], wherein —CH ₂ CH ₂ — or —C≡C—; and m is an integer of 1 to 3.

[4] The polymerizable liquid crystal compound according to the item [1] or [2], wherein Z ¹ is a single bond, —COO— or —OCO—; and m is 1 or 2.

[5] P ² is a polymerizable group represented by any one of formulas (2-1) to (2-4); Q ¹ is —COO—, —OCO—, or C 2-14. Any hydrogen in the alkylene may be replaced by fluorine, and any —CH ₂ — may be —O—, —COO—, —OCO—, —CH═CH— or —C≡C May be replaced by-;
When P ² is a polymerizable group represented by the formula (2-2), Q ² is alkylene having 1 to 14 carbon atoms in which any —CH ₂ — may be replaced by —O—, Any hydrogen in alkylene may be replaced by fluorine; when P ² is a polymerizable group represented by formula (2-1), formula (2-3) or formula (2-4), Q ² is a group defined the same as Q ^1, [1] ~ polymerizable liquid crystal compound according to any one of [4].

[6] P ² is a polymerizable group represented by any one of formulas (2-1) to (2-4); Q ¹ is —COO—, —OCO—, or C 2-14. And any —CH ₂ — in the alkylene may be replaced by —O—, —COO— or —OCO—;
When P ² is a polymerizable group represented by formula (2-2), Q ² is alkylene having 1 to 14 carbon atoms in which any —CH ₂ — may be replaced by —O—; ^{When 2} is a polymerizable group represented by formula (2-1), formula (2-3) or formula (2-4), Q ² is a group defined in the same manner as Q ¹ ; [1] The polymerizable liquid crystal compound according to any one of [4].

[7] The polymerizable liquid crystal compound according to any one of [1] to [6], wherein R ^a in formula (2-2) to formula (2-4) is independently hydrogen, methyl or ethyl. .

[8] A ¹ and A ² are independently 1,4-cyclohexylene, 1,4-phenylene, naphthalene-2,6-diyl or fluorene-2,7-diyl. And any hydrogen in fluorene-2,7-diyl may be replaced by fluorine, methyl or trifluoromethyl; Z ¹ is a single bond, —COO—, —OCO—, —CH═CH—COO—, — CH ₂ CH ₂ —COO—, —OCO—CH═CH—, —OCO—CH ₂ CH ₂ —, —CH ₂ CH ₂ — or —C≡C—; m is an integer from 1 to 3; P ² is a polymerizable group represented by any one of formulas (2-1) to (2-4); Q ¹ is —COO—, —OCO—, or alkylene having 2 to 14 carbon atoms. Any hydrogen in this alkylene is May be replaced by, arbitrary _-CH 2 - -O -, - COO -, - OCO -, - may be replaced by CH = CH- or -C≡C-;
When P ² is a polymerizable group represented by the formula (2-2), Q ² is alkylene having 1 to 14 carbon atoms in which any —CH ₂ — may be replaced by —O—, Any hydrogen in alkylene may be replaced by fluorine; when P ² is a polymerizable group represented by formula (2-1), formula (2-3) or formula (2-4), Q ² is a group defined as in Q ¹ ;
The polymerizable liquid crystal compound according to item [1], wherein R ^a in formula (2-2) to formula (2-4) is independently hydrogen, methyl or ethyl.

[9] A ¹ and A ² are independently 1,4-cyclohexylene or 1,4-phenylene, and any one or two hydrogens in 1,4-phenylene are replaced by fluorine or methyl Z ¹ is a single bond, —COO— or —OCO—; m is 1 or 2; and P ² is any one of formulas (2-1) to (2-4) Q ¹ is —COO—, —OCO—, or alkylene having 2 to 14 carbon atoms, and any —CH ₂ — in the alkylene is —O—, —COO— or —. May be replaced by OCO-;
When P ² is a polymerizable group represented by formula (2-2), Q ² is alkylene having 1 to 14 carbon atoms in which any —CH ₂ — may be replaced by —O—; ^{When 2} is a polymerizable group represented by formula (2-1), formula (2-3) or formula (2-4), Q ² is a group defined in the same manner as Q ¹ ;
The polymerizable liquid crystal compound according to item [1], wherein R ^a in formula (2-2) to formula (2-4) is independently hydrogen, methyl or ethyl.

[10] A ¹ and A ² are independently 1,4-cyclohexylene or 1,4-phenylene, and any one or two hydrogens in the 1,4-phenylene are replaced by fluorine or methyl Z ¹ is a single bond, —COO— or —OCO—; m is 1 or 2; P ² is a polymerizable group represented by formula (2-1); and Q ¹ and Q ² is independently —COO—, —OCO—, or an arbitrary —CH ₂ — is alkylene having 2 to 14 carbon atoms, which may be replaced by —O—, —COO— or —OCO—, [ The polymerizable liquid crystal compound according to item 1].

[11] A ¹ and A ² are independently 1,4-cyclohexylene or 1,4-phenylene, and any one or two hydrogens in 1,4-phenylene are replaced by fluorine or methyl Z ¹ is a single bond, —COO— or —OCO—; m is 1 or 2; P ² is a polymerizable group represented by formula (2-2); and Q ¹ is -COO -, - it is OCO- or alkylene having a carbon number of 2 to 14, any -CH ₂ - in the alkylene may -O -, - COO- or -OCO- may be replaced by; ^{Q 2} is The polymerizable liquid crystal according to item [1], wherein arbitrary —CH ₂ — is alkylene having 1 to 14 carbon atoms which may be replaced by —O—; ^Ra in formula (2-2) is hydrogen. Compound.

[12] A ¹ and A ² are independently 1,4-cyclohexylene or 1,4-phenylene, and any one or two hydrogens in the 1,4-phenylene are replaced by fluorine or methyl Z ¹ is a single bond, —COO— or —OCO—; m is 1 or 2; P ² is a polymerizable group represented by formula (2-3); and Q ¹ and Q ² is independently —COO—, —OCO— or alkylene having 2 to 14 carbon atoms, and any —CH ₂ — in the alkylene is replaced by —O—, —COO— or —OCO—. The polymerizable liquid crystal compound according to item [1], wherein R ^a in formula (2-3) is hydrogen.

[13] A ¹ and A ² are independently 1,4-cyclohexylene or 1,4-phenylene, and any one or two hydrogens in 1,4-phenylene are replaced by fluorine or methyl Z ¹ is a single bond, —COO— or —OCO—; m is 1 or 2; P ² is a polymerizable group represented by formula (2-4); and Q ¹ and Q ² is independently —COO—, —OCO— or alkylene having 2 to 14 carbon atoms, and any —CH ₂ — in the alkylene is replaced by —O—, —COO— or —OCO—. The polymerizable liquid crystal compound according to item [1], wherein R ^a in formula (2-4) is methyl or ethyl.

ここに、Ａ^１およびＡ^２は独立して１，４−シクロへキシレン、１，４−フェニレン、ピリジン−２，５−ジイル、ピリミジン−２，５−ジイル、ナフタレン−２，６−ジイル、テトラヒドロナフタレン−２，６−ジイル、１，３−ジオキサン−２，５−ジイルまたはフルオレン−２，７−ジイルであり；この１，４−フェニレンおよびフルオレン−２，７−ジイルにおいて、任意の水素はフッ素、塩素、シアノ、メチル、エチル、メトキシ、ヒドロキシ、ホルミル、アセトキシ、アセチル、トリフルオロアセチル、ジフルオロメチルまたはトリフルオロメチルで置き換えられてもよく；Ｚ^１は単結合、−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＨ＝ＣＨ−ＣＯＯ−、−ＯＣＯ−ＣＨ＝ＣＨ−、−ＯＣＯ−ＣＨ_２ＣＨ_２−、−ＣＨ_２ＣＨ_２−ＣＯＯ−、−Ｃ≡Ｃ−ＣＯＯ−、−ＯＣＯ−Ｃ≡Ｃ−、−ＣＨ_２Ｏ−、−ＯＣＨ_２−、−ＣＦ_２Ｏ−、−ＯＣＦ_２−、−ＣＯＮＨ−、−ＮＨＣＯ−、−（ＣＨ_２）_４−、−ＣＨ_２ＣＨ_２−、−ＣＦ_２ＣＦ_２−、−ＣＨ＝ＣＨ−、−ＣＦ＝ＣＦ−または−Ｃ≡Ｃ−であり；ｍは０〜５の整数であり；ｍが２以上であるとき、環Ａ^２の任意の２つは同じであってもよく、または異なってもよく、Ｚ^１の任意の２つは同じであってもよく、または異なってもよく；Ｐ^１は式（２−１）で表される重合性基であり；Ｑ^１は炭素数１〜２０のアルキレンであり、このアルキレン中の任意の水素はフッ素で置き換えられてもよく、任意の−ＣＨ_２−は−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられてもよく；Ｐ^２は式（２−１）〜式（２−４）のいずれか１つで表される重合性基、水素、フッ素、シアノ、トリフルオロメチル、トリフルオロメトキシ、炭素数１〜２０のアルキル、または炭素数１〜２０のアルコキシであり；Ｑ^２は、Ｐ^２が重合性基であるときＱ^１と同じように定義される基であり、Ｐ^２が重合性基でないときは単結合であり：

ここに、Ａ^３およびＡ^４は独立して１，４−シクロへキシレン、１，４−フェニレン、ナフタレン−２，６−ジイル、フルオレン−２，７−ジイルまたは１，３−ジオキサン−２，５−ジイルであり；この１，４−フェニレンおよびフルオレン−２，７−ジイルにおいて、任意の水素はフッ素または塩素で置き換えられてもよく、そして任意の水素はシアノ、メチル、エチル、メトキシ、ヒドロキシ、ホルミル、アセトキシ、アセチル、トリフルオロアセチル、ジフルオロメチル、またはトリフルオロメチルで置き換えられてもよく；Ｚ^２は独立して単結合、−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＨ＝ＣＨ−ＣＯＯ−、−ＯＣＯ−ＣＨ＝ＣＨ−、−ＯＣＯ−ＣＨ_２ＣＨ_２−、−ＣＨ_２ＣＨ_２−ＣＯＯ−、−Ｃ≡Ｃ−ＣＯＯ−、−ＯＣＯ−Ｃ≡Ｃ−、−ＣＨ_２Ｏ−、−ＯＣＨ_２−、−ＣＦ_２Ｏ−、−ＯＣＦ_２−、−ＣＯＮＨ−、−ＮＨＣＯ−、−（ＣＨ_２）_４−、−ＣＨ_２ＣＨ_２−、−ＣＦ_２ＣＦ_２−、−ＣＨ＝ＣＨ−、−ＣＦ＝ＣＦ−、または−Ｃ≡Ｃ−であり；ｎは０〜５の整数であり；ｎが２以上であるとき、環Ａ^４の任意の２つは同じであってもよく、または異なってもよく、Ｚ^２の任意の２つは同じであってもよく、または異なってもよく；Ｑ^３およびＱ^４は独立して炭素数１〜２０のアルキレンであり、このアルキレン中の任意の水素はフッ素で置き換えられてもよく、任意の−ＣＨ_２−は−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられてもよく；Ｒはフッ素、シアノ、トリフルオロメチル、トリフルオロメトキシ、炭素数１〜２０のアルキル、または炭素数１〜２０のアルコキシであり；Ｐ^３およびＰ^４は独立して式（２−２）〜式（２−４）のいずれか１つで表される重合性基であり、式（２−２）〜式（２−４）におけるＲ^ａは独立して水素、ハロゲン、または炭素数１〜５のアルキルである。 [14] Contains at least one polymerizable liquid crystal compound represented by formula (1) and at least one compound selected from the group of polymerizable liquid crystal compounds represented by formula (M1) and formula (M2). Polymerizable liquid crystal composition:

Wherein A ¹ and A ² are independently 1,4-cyclohexylene, 1,4-phenylene, pyridine-2,5-diyl, pyrimidine-2,5-diyl, naphthalene-2,6-diyl, Tetrahydronaphthalene-2,6-diyl, 1,3-dioxane-2,5-diyl or fluorene-2,7-diyl; in this 1,4-phenylene and fluorene-2,7-diyl, any hydrogen May be replaced by fluorine, chlorine, cyano, methyl, ethyl, methoxy, hydroxy, formyl, acetoxy, acetyl, trifluoroacetyl, difluoromethyl or trifluoromethyl; Z ¹ is a single bond, —O—, —COO -, - OCO -, - CH = CH-COO -, - OCO-CH = CH -, - OCO-CH 2 CH 2 -, - CH 2 CH ₂ -COO—, —C≡C—COO—, —OCO—C≡C—, —CH ₂ O—, —OCH ₂ —, —CF ₂ O—, —OCF ₂ —, —CONH—, —NHCO— , — (CH ₂ ) ₄ —, —CH ₂ CH ₂ —, —CF ₂ CF ₂ —, —CH═CH—, —CF═CF— or —C≡C—; m is an integer of 0 to 5 And when m is 2 or more, any ^two of ring A ² may be the same or different, and any two of Z ¹ may be the same or different P ¹ is a polymerizable group represented by the formula (2-1); Q ¹ is an alkylene having 1 to 20 carbon atoms, and any hydrogen in the alkylene may be replaced by fluorine. well, arbitrary _-CH 2 - -O -, - COO -, - OCO -, - replaced by CH = CH- or -C≡C- It may be; ^{P 2} is a polymerizable group represented by any one formula (2-1) to formula (2-4), hydrogen, fluorine, cyano, trifluoromethyl, trifluoromethoxy, carbon atoms 1-20 alkyl, or a C 1 -C 20 alkoxy; ^{Q 2} is a group defined the same as ^{Q 1} when ^{P 2} is a polymerizable group, not ^{P 2} is a polymerizable group Sometimes it is a single bond:

Where A ³ and A ⁴ are independently 1,4-cyclohexylene, 1,4-phenylene, naphthalene-2,6-diyl, fluorene-2,7-diyl or 1,3-dioxane-2, In this 1,4-phenylene and fluorene-2,7-diyl, any hydrogen may be replaced by fluorine or chlorine, and any hydrogen may be cyano, methyl, ethyl, methoxy, hydroxy , Formyl, acetoxy, acetyl, trifluoroacetyl, difluoromethyl, or trifluoromethyl; Z ² is independently a single bond, —O—, —COO—, —OCO—, —CH═CH _{-COO -, - OCO-CH =} CH -, - OCO-CH 2 CH 2 -, - CH 2 CH 2 -COO -, - C≡C-COO -, - O _{O-C≡C -, - CH 2} O -, - OCH 2 -, - CF 2 O -, - OCF 2 -, - CONH -, - NHCO -, - (CH 2) 4 -, - CH 2 CH 2 _{-, - CF 2 CF 2 -} , - CH = CH -, - CF = CF-, or a -C≡C-; n is an integer from 0 to 5; when n is 2 or more, the ring a Any two of ⁴ may be the same or different, any ^two of Z ² may be the same or different; Q ³ and Q ⁴ are independently An alkylene having 1 to 20 carbon atoms, and any hydrogen in the alkylene may be replaced by fluorine, and any —CH ₂ — may be —O—, —COO—, —OCO—, —CH═CH—; Or -C≡C-; R may be fluorine, cyano, trifluoromethyl, trifluoro Any one Tsudehyo of ^{P 3} and ^{P 4} are each independently formula (2-2) to (2-4); methoxy, alkyl of 1 to 20 carbons or alkoxy having 1 to 20 carbon atoms R ^a in formula (2-2) to formula (2-4) is independently hydrogen, halogen, or alkyl having 1 to 5 carbon atoms.

[15] In the formula (1), A ¹ and A ² are independently 1,4-cyclohexylene, 1,4-phenylene, naphthalene-2,6-diyl, or fluorene-2,7-diyl. In this 1,4-phenylene and fluorene-2,7-diyl, any hydrogen may be replaced by fluorine, methyl or trifluoromethyl; Z ¹ is a single bond, —COO—, —OCO—, —CH ═CH—COO—, —CH ₂ CH ₂ —COO—, —OCO—CH═CH—, —OCO—CH ₂ CH ₂ —, —CH ₂ CH ₂ — or —C≡C—; be to 3 integer; ^{P 2} is located at the polymerizable group represented by any one formula (2-1) to formula (2-4); ^{Q 1} is -COO -, - OCO- or carbon An alkylene having a number of 2 to 14, and this alkyle Arbitrary hydrogen may be replaced by fluorine and arbitrary _-CH 2 in - is -O -, - COO -, - OCO -, - may be replaced by CH = CH- or -C≡C- When P ² is a polymerizable group represented by the formula (2-2), Q ² is alkylene having 1 to 14 carbon atoms in which arbitrary —CH ₂ — may be replaced by —O—; Any hydrogen in this alkylene may be replaced by fluorine; when P ² is a polymerizable group represented by formula (2-1), formula (2-3) or formula (2-4), Q ² is a group defined in the same manner as Q ¹ ; R ^a in formula (2-2) to formula (2-4) is independently hydrogen, methyl or ethyl:
In Formula (M1) and Formula (M2), A ³ and A ⁴ are independently 1,4-cyclohexylene or 1,4-phenylene, and any one or two of the 1,4-phenylene Hydrogen may be replaced by fluorine, methyl or trifluoromethyl; Z ² is independently a single bond, —O—, —COO—, or —OCO—; n is an integer from 1 to 3; Q ³ and Q ⁴ are each independently alkylene having 1 to 14 carbons, and any hydrogen in the alkylene may be replaced by fluorine, and any —CH ₂ — may be —O—, —COO— or -OCO- may be substituted; in formula (2-2) to formula (2-4), Ra is independently hydrogen, methyl or ethyl:
Based on the total amount of the compound selected from the group consisting of the polymerizable liquid crystal compound represented by formula (1) and the polymerizable liquid crystal compound represented by formula (M1) and formula (M2), the formula (1) The ratio of the polymerizable compound represented by the formula is 5 to 95% by weight, and the ratio of the compound selected from the group of the polymerizable compounds represented by the formula (M1) and the formula (M2) is 5 to 95% by weight. The polymerizable liquid crystal composition according to item [14].

[16] In the formula (1), A ¹ and A ² are independently 1,4-cyclohexylene or 1,4-phenylene, and any one or two hydrogens in the 1,4-phenylene are May be replaced by fluorine or methyl; Z ¹ is a single bond, —COO— or —OCO—; m is 1 or 2; and P ² is represented by formula (2-1) to formula (2-4) Q ¹ is —COO—, —OCO—, or alkylene having 2 to 14 carbons, and any —CH ₂ — in the alkylene is —O—. , —COO— or —OCO— may be substituted; when P ² is a polymerizable group represented by the formula (2-2), Q ² may be replaced with any —CH ₂ — with —O—. C 1-14 alkylene which may be substituted; P ² is of formula (2- 1), when it is a polymerizable group represented by formula (2-3) or formula (2-4), Q ² is a group defined in the same manner as Q ¹ ; formula (2-2) to R ^a in formula (2-4) is independently hydrogen, methyl or ethyl:
In Formula (M1) and Formula (M2), A ³ and A ⁴ are independently 1,4-cyclohexylene or 1,4-phenylene, and any one or two of the 1,4-phenylene Hydrogen may be replaced by fluorine, methyl or trifluoromethyl; Z ² is independently a single bond, —O—, —COO— or —OCO—; n is 1 or 2; Q ³ and Q ⁴ is independently alkylene having 1 to 14 carbons, and any hydrogen in the alkylene may be replaced by fluorine, and any —CH ₂ — may be —O—, —COO— or —OCO—. R ^a in formula (2-2) to formula (2-4) is independently hydrogen, methyl or ethyl:
Based on the total amount of the compound selected from the group consisting of the polymerizable liquid crystal compound represented by formula (1) and the polymerizable liquid crystal compound represented by formula (M1) and formula (M2), the formula (1) The ratio of the polymerizable liquid crystal compound represented by the formula is 10 to 90 wt%, and the ratio of the compound selected from the group of the polymerizable liquid crystal compounds represented by the formula (M1) and the formula (M2) is 10 to 90 wt%. The polymerizable liquid crystal composition according to item [14], wherein

[17] Based on the total amount of the compound selected from the group consisting of the polymerizable liquid crystal compound represented by formula (1) and the polymerizable liquid crystal compound represented by formula (M1) and formula (M2), the formula (1 ) Is 30 to 80% by weight, and the proportion of the compound selected from the group of polymerizable liquid crystal compounds represented by formula (M1) and formula (M2) is 20 to 70% by weight. %, The polymerizable liquid crystal composition according to any one of [15] to [16].

[18] Based on the total amount of the compound selected from the group consisting of the polymerizable liquid crystal compound represented by formula (1) and the polymerizable liquid crystal compound represented by formula (M1) and formula (M2), the formula (1 ) Is 40 to 70 wt%, and the proportion of the compound selected from the group of polymerizable liquid crystal compounds represented by formula (M1) and formula (M2) is 30 to 60 wt%. %, The polymerizable liquid crystal composition according to any one of [14] to [16].

[19] The polymerizable liquid crystal composition according to any one of [14] to [18], further containing another polymerizable liquid crystal compound.

[20] The polymerizable liquid crystal composition according to any one of [14] to [19], further containing a polymerizable optically active compound.

[21] The polymerizable liquid crystal composition according to any one of [14] to [20], further containing a non-polymerizable liquid crystal compound.

[22] The polymerizable liquid crystal composition according to any one of [14] to [21], further containing a non-polymerizable optically active compound.

[23] A film having optical anisotropy containing a polymer obtained by polymerizing at least one of the compounds according to any one of [1] to [13].

[24] A film having optical anisotropy obtained by polymerizing the polymerizable liquid crystal composition according to any one of [14] to [22].

[25] The film having optical anisotropy according to the item [23] or [24], which has optical properties of an A plate.

[26] The film having optical anisotropy according to the item [23] or [24], which has optical properties of a C plate.

[27] The film having optical anisotropy according to the item [23] or [24], which has optical properties of a negative C plate.

[28] The film having optical anisotropy according to the item [23] or [24], which has optical characteristics of an O plate.

[29] A liquid crystal display device comprising the film having optical anisotropy according to any one of [23] to [28].

  The compound (1) of the present invention is characterized by being extremely physically and chemically stable under conditions usually used and having high solubility in a polar solvent. By appropriately selecting the ring, bonding group, and side chain constituting the compound of the present invention, adjustments such as optical anisotropy (Δn) and viscosity level can be appropriately made. Even if the atom constituting the compound of the present invention is its isotope, it can be preferably used because it exhibits the same characteristics.

  Compound (1) is easily cured in air because the polymerization mode is a cationic polymerization reaction. Since the monofunctional compound has a high degree of freedom in selecting substituents, the optical properties of the composition and the solubility in a solvent can be controlled. In addition, since the bifunctional compound has a stronger cross-link structure than the monofunctional compound, the polymer has higher heat resistance, lower water absorption, water permeability and gas permeability. The mechanical strength (particularly hardness) is higher. Furthermore, a compound having a cyclohexene oxide moiety as a polymerizable group has a feature that its solubility in a safety solvent is higher than that of an epoxy compound. An example of the safety solvent is PGMEA (polyethylene glycol monomethyl ether acetate), but is not limited thereto.

The polymerizable liquid crystal compound of the present invention is represented by the formula (1).

A ¹ and A ² are independently 1,4-cyclohexylene, 1,4-phenylene, pyridine-2,5-diyl, pyrimidine-2,5-diyl, naphthalene-2,6-diyl, tetrahydronaphthalene- 2,6-diyl, 1,3-dioxane-2,5-diyl or fluorene-2,7-diyl. In this 1,4-phenylene and fluorene-2,7-diyl, any hydrogen is fluorine, chlorine, cyano, methyl, ethyl, methoxy, hydroxy, formyl, acetoxy, acetyl, trifluoroacetyl, difluoromethyl or tri It may be replaced with fluoromethyl. Preferred A ¹ and A ² are independently 1,4-cyclohexylene, 1,4-phenylene, naphthalene-2,6-diyl, or fluorene-2,7-diyl, and the 1,4-phenylene and Any one or two hydrogens in fluorene-2,7-diyl may be replaced with fluorine, methyl or trifluoromethyl. More preferably, A ¹ and A ² are independently 1,4-cyclohexylene or 1,4-phenylene, and any one or two hydrogens in 1,4-phenylene are fluorine or methyl. May be replaced. Preferred examples of A ¹ and A ² are 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene, 2,5-difluoro. -1,4-phenylene, 2,6-difluoro-1,4-phenylene, 2-methyl-1,4-phenylene, 3-methyl-1,4-phenylene, and 2,3-dimethyl-1,4- Phenylene.
When both A ¹ and A ² are 1,4-phenylene, the melting point is high, the clearing point tends to be high, and the temperature range of the liquid crystal phase tends to be widened, and at least one of A ¹ and A ² is 1,4-cyclohexane. In the case of hexylene, the temperature range of the liquid crystal phase tends to be narrow, but the optical anisotropy tends to be small.

The bonding group Z ¹ is a single bond, —O—, —COO—, —OCO—, —CH═CH—COO—, —OCO—CH═CH—, —OCO—CH ₂ CH ₂ —, —CH ₂ CH _2. —COO—, —C≡C—COO—, —OCO—C≡C—, —CH ₂ O—, —OCH ₂ —, —CF ₂ O—, —OCF ₂ —, —CONH—, —NHCO—, _{- (CH 2) 4 -,} - CH 2 CH 2 -, - CF 2 CF 2 -, - CH = CH -, - a CF = CF- or -C≡C-. Z ¹ is a single bond, —CH ₂ CH ₂ —, —CH ₂ O—, —OCH ₂ —, —CF ₂ O—, —OCF ₂ —, —CH═CH—, —CF═CF— or — (CH ₂₎ 4 _-, the tend to viscosity of the compound (1) is reduced. When Z ¹ is —CH═CH— or —CF═CF—, the temperature range of the liquid crystal phase of compound (1) is wide and the elastic constant ratio tends to be large. When Z ¹ is -C≡C-, it tends to optical anisotropy of the film obtained by polymerizing the compound (1) increases.

m is an integer of 0 to 5, preferably an integer of 1 to 3. Particularly preferred m is 1 or 2. When m is 2 or more, any ^two of the ring A ² may be the same or different, and any two of Z ¹ may be the same or different .

式（２−２）〜式（２−４）におけるＲ^aは、独立して水素、ハロゲン、または炭素数１〜５のアルキルであり、独立して水素、メチルまたはエチルであることが好ましい。Ｐ^１およびＰ^２が共に式（２−１）で表される重合性基であるとき、化合物（１）の有機溶剤への溶解度が高くなり、化合物（１）を重合させる場合の重合速度に優れる傾向がある。Ｐ^２が式（２−３）であるとき化合物（１）を重合させて得られるフィルムの硬度に優れる傾向がある。Ｐ^２が式（２−４）で表される重合性基であるとき、化合物（１）は有機溶剤への溶解度に優れ、融点や透明点が下がる傾向がある。 P ¹ is a polymerizable group represented by the formula (2-1). P ² is a polymerizable group represented by any one of formulas (2-1) to (2-4), hydrogen, fluorine, cyano, trifluoromethyl, trifluoromethoxy, alkyl having 1 to 20 carbon atoms. Or an alkoxy group having 1 to 20 carbon atoms, and preferably a polymerizable group represented by any one of formulas (2-1) to (2-4).

R ^a in formula (2-2) to formula (2-4) is independently hydrogen, halogen, or alkyl having 1 to 5 carbon atoms, and is preferably independently hydrogen, methyl, or ethyl. When both P ¹ and P ² are polymerizable groups represented by the formula (2-1), the solubility of the compound (1) in the organic solvent is increased, and the polymerization rate when the compound (1) is polymerized is increased. There is a tendency to excel. P ² tends to excellent hardness of the film obtained by polymerizing the compound (1) When an expression (2-3). When P ² is a polymerizable group represented by the formula (2-4), the compound (1) is excellent in solubility in an organic solvent and tends to lower the melting point and the clearing point.

Q ¹ is alkylene having 1 to 20 carbon atoms, and any hydrogen in the alkylene may be replaced by fluorine, and any —CH ₂ — represents —O—, —COO—, —OCO—, —CH ═CH— or —C≡C— may be substituted. Q ¹ is preferably —COO—, —OCO— or alkylene having 2 to 14 carbon atoms, and in this case, any hydrogen in the alkylene may be replaced by fluorine, and any —CH ₂ — is -O-, -COO-, -OCO-, -CH = CH-, or -C≡C- may be substituted. Q ¹ is more preferably C 2 -C 14 alkylene, —COO—, —OCO—, or any —CH ₂ — in which —O—, —COO— or —OCO— may be substituted. preferable. When Q ¹ is alkylene, linear alkylene is preferable to branched alkylene.

Q ² is a group P ² is defined the same as Q ¹ when a polymerizable group, when P ² is not a polymerizable group is a single bond. Q ² is a group in which P ² is a polymerizable group represented by the formula (2-2), and arbitrary —CH ₂ — may be replaced with —O—, and arbitrary hydrogen is replaced with fluorine. It is preferably an alkylene having 1 to 14 carbon atoms, and more preferably an alkylene having 1 to 14 carbon atoms in which arbitrary —CH ₂ — may be replaced by —O—. When P ² is a polymerizable group represented by formula (2-1), formula (2-3) or formula (2-4), Q ² is defined in the same manner as Q ¹ as described above. It is a group. When the chain length of the alkylene for Q ¹ and Q ² is long, the compound (1) tends to exhibit a broad liquid crystal temperature range, the introduction of oxygen into the alkylene tends to solubility in polar solvents is improved. When Q ¹ is —COO—, the compound (1) tends to exhibit a high liquid crystal temperature region.

  As described above, the compound (1) having the desired physical properties can be obtained by appropriately selecting the type of polymerizable group, ring and bonding group, and the number of rings. Compound (1) can be synthesized by combining organic synthetic chemistry techniques. Methods for introducing the desired end groups, rings and linking groups into the starting material are described by Houben-Wyle, Methods of Organic Chemistry, Georg Thieme Verlag, Stuttgart, Organic Syntheses, John Wily & Sons. , Inc.), Organic Reactions (John Wily & Sons Inc.), Comprehensive Organic Synthesis (Pergamon Press), New Experimental Chemistry Course (Maruzen), etc. ing. In the schemes shown below, the meanings of symbols not specifically described are as described above.

The synthesis of the linking group Z ¹ is described in Schemes 1-13. In this scheme, MSG ¹ and MSG ² are monovalent organic groups having at least one ring. A plurality of MSG ¹ (or MSG ² ) may be the same or different. Compounds (1A) to (1L) correspond to compound (1) of the present invention.

<Scheme 1> Compound in which bonding group Z ¹ is a single bond As shown below, arylboric acid (S1) and compound (S2) synthesized by a known method are mixed with tetrakis (triphenylphosphine) in an aqueous carbonate solution. Compound (1A) can be synthesized by reacting in the presence of a catalyst such as palladium. This compound (1A) is obtained by reacting compound (S3) synthesized by a known method with n-butyllithium and then with zinc chloride, and then in the presence of a catalyst such as dichlorobis (triphenylphosphine) palladium. It can also be synthesized by further reacting with S2).

<Scheme 2> Compound in which linking group Z ¹ is —CH═CH— As shown below, phosphorus ylide generated by adding a base such as potassium t-butoxide to a phosphonium salt (S5) synthesized by a known method Is reacted with aldehyde (S4) to synthesize compound (1B). Since a cis isomer is generated depending on reaction conditions and substrates, the cis isomer is isomerized to a trans isomer by a known method as necessary.

<Scheme 3> Compound in which linking group Z ¹ is —CH ₂ CH ₂ — As shown below, compound (1C) can be synthesized by hydrogenating compound (1B) in the presence of a catalyst such as palladium carbon. .

<Scheme 4> Compound in which linking group Z ¹ is —CF ₂ CF ₂ — As shown below, the presence of a hydrogen fluoride catalyst according to the method described in J. Am. Chem. Soc., 2001, 123, 5414 The compound (1D) having — (CF ₂ ) ₂ — can be synthesized by fluorinating the diketone (S6) with sulfur tetrafluoride.

<Scheme 5> Compound in which linking group Z ¹ is — (CH ₂ ) ₄ — As shown below, according to the method of Scheme 2, using phosphonium salt (S7) instead of phosphonium salt (S5), —CH ₂ CH Compound (1E) can be synthesized by synthesizing a compound having ₂ -CH═CH— and catalytically hydrogenating the compound.

<Scheme 6> Compound in which bonding group Z ¹ is —CH ₂ O— or —OCH ₂ — As shown below, compound (S4) is first reduced with a reducing agent such as sodium borohydride to give compound (S8). Get. This is halogenated with hydrobromic acid or the like to obtain compound (S9). Next, compound (1F) can be synthesized by reacting compound (S9) with compound (S10) in the presence of potassium carbonate or the like. A compound having —CH ₂ O— can also be synthesized by this method.

<Scheme 7> Compound in which linking group Z ¹ is —COO— or —OCO— As shown below, carboxylic acid (S11) is obtained by reacting compound (S3) with n-butyllithium and then with carbon dioxide. Compound (1G) having —COO— can be synthesized by dehydrating compound (S11) and phenol (S10) in the presence of DCC (1,3-dicyclohexylcarbodiimide) and DMAP (4-dimethylaminopyridine). . A compound having —OCO— can also be synthesized by this method. Alternatively, (1G) can be synthesized by reacting (S11) with thionyl chloride or oxalyl chloride to induce an acid chloride compound and reacting with (S10) in the presence of a base such as pyridine or triethylamine. .

<Scheme 8> Compound in which bonding group Z ¹ is —CF═CF— As shown below, compound (S3) is first treated with n-butyllithium and then reacted with tetrafluoroethylene to give compound (S12). obtain. Next, after treating the compound (S2) with n-butyllithium, the compound (1H) can be synthesized by reacting with the compound (S12). By selecting the reaction conditions, the cis-form compound (1H) can also be produced.

<Scheme 9> Compound in which bonding group Z ¹ is —C≡C— As shown below, compound (S12) is reacted with compound (S2) in the presence of a catalyst of dichloropalladium and copper halide to give compound ( 1I) can be synthesized.

<Scheme 10> Compound in which bonding group Z ¹ is —C≡C—COO— As shown below, compound (S12) is first lithiated with n-butyllithium, and then reacted with carbon dioxide to react with carboxylic acid ( S13) is obtained. Subsequently, the compound (J) having —C≡C—COO— can be synthesized by dehydrating the carboxylic acid (S13) and the phenol (S10) in the presence of DCC and DMAP. A compound having —OCO—C≡C— can also be synthesized by this method. Moreover, (1J) can also be synthesized via an acid chloride compound as derived from (S11) to (1G) in Scheme 7.

<Scheme 11> Compound in which Z ¹ is —CF ₂ O— or —OCF ₂ — As shown below, compound (1G) is first treated with a sulfurizing agent such as Lawesson's reagent to give compound (S14). obtain. Next, the compound (1K) having —CF ₂ O— can be synthesized by fluorinating the compound (S14) using a hydrogen fluoride pyridine complex and NBS (N-bromosuccinimide). The compound (1K) can also be synthesized by fluorinating the compound (S14) with (diethylamino) sulfur trifluoride (DAST). A compound having —OCF ₂ — can also be synthesized by this method. These linking groups can also be generated by the method described in P. Kirsch et al., Angew. Chem. Int. Ed. 2001, 40, 1480.

A method for introducing a polymerizable group will be described in Schemes 12 and 13. In these schemes, MSG is a monovalent organic group having at least one ring. The plurality of MSGs may be the same or different. Y is alkylene having 1 to 21 carbon atoms, and any hydrogen in the alkylene may be replaced by fluorine or chlorine, and any —CH ₂ — may be —O—, —COO—, —OCO—, — It may be replaced by CH═CH— or —C≡C—. P is a polymerizable group represented by any one of the above formulas (2-1) to (2-4). Compound (1L) corresponds to compound (1) of the present invention.

<Scheme 12> When introducing from a polymerizable group As shown below, a diol (T1) and a compound (T2) synthesized by a known method are reacted with a base such as sodium hydride to form a monoether The body (T3) is synthesized. This is tosylated with p-toluenesulfonic acid chloride to obtain (T4). Next, compound (1L) can be synthesized by reacting tosylate (T4) with (S10) using a base such as potassium carbonate. This compound is obtained by reacting a compound (T5) synthesized by a known method with an alcohol (T6) having a polymerizable group using a base such as sodium hydroxide, and then obtaining a monoether (T7). It can also be synthesized by reacting the monoether derivative (T7) with (S10) using a base such as potassium carbonate.

<Scheme 13> Introducing a polymerizable group later As shown below, by reacting (S10) with a compound (T8) synthesized by a known method using a base such as potassium carbonate, An ether form (T9) can be synthesized. Next, the compound (1L) can be synthesized by reacting the monoether form (T9) and (T2) with a base such as sodium hydroxide.

  Compound (1) can be synthesized by appropriately combining the above methods, but is not necessarily limited to the above methods. Examples of compounds synthesized by the above method are shown below. The structure of the compound synthesized as described above can be confirmed by, for example, a proton NMR spectrum.

Next, the polymerizable liquid crystal composition of the present invention will be described. The composition of the present invention contains at least one compound (1). In addition, the composition of the present invention may contain at least one compound selected from the group consisting of at least one of compound (1) and compound (M1) and compound (M2). Compound (M1) exhibits a wide liquid crystal phase and has two polymerizable groups in its structure, so it can form a three-dimensional network structure and can form a polymer with high mechanical strength. It becomes. Since the compound (M2) has one polymerizable group and has a substituent such as a polar group on the opposite side of the polymerizable group in the molecular long axis direction, the alignment control in the liquid crystal state can be adjusted. . In both the compound (M1) and the compound (M2), when ring A ³ is 1,4-phenylene, a composition having high optical anisotropy (Δn) is used as naphthalene-2,6-diyl or fluorene. In the case of -2,7-diyl, a composition having a higher optical anisotropy (Δn) can be prepared, and in the case of 1,4-cyclohexylene, a composition having a low optical anisotropy (Δn) can be prepared. it can.

Preferable examples of the compounds (M1) and (M2) include the compounds shown below.

In these compounds, ^{Q 3} and ^{Q 4} have the same meanings as ^{Q 3} and ^{Q 4} in the formula (M1) and formula (M2), ^{P 3} and ^{P 4} above formulas independently (2-2 ) To a group represented by any one of formulas (2-4).

  In the following description, the compound (M1) and the compound (M2) are collectively referred to as the compound (M). The polymerizable liquid crystal composition of the present invention contains at least one compound (1). Moreover, the polymerizable liquid crystal composition of the present invention may contain at least one of the compound (1) and at least one of the compound (M). A preferred content ratio of the compound (1) in the polymerizable liquid crystal composition of the present invention is 5 to 95% by weight based on the total amount of the compound (1) and the compound (M). A more preferable ratio is 10 to 90% by weight, a further preferable ratio is 30 to 80% by weight, and a particularly preferable ratio is 40 to 70% by weight. A preferable content ratio of the compound (M) is 5 to 95% by weight based on the total amount of the compound (1) and the compound (M). A more preferable ratio is 10 to 90% by weight, a further preferable ratio is 20 to 70% by weight, and a particularly preferable ratio is 30 to 60% by weight. The polymerizable liquid crystal composition of the present invention contains the compound (1) and the compound (M) as polymerizable compounds, but may further contain other polymerizable compounds. This polymerizable liquid crystal composition may contain a non-polymerizable compound, an additive, a solvent, and the like. Examples of non-polymerizable compounds are the compounds described in Liquist, a database of liquid crystalline compounds (LiqCryst, LCI Publisher GmbH, Hamburg, Germany). Examples of the additive include a nonionic surfactant, a photocationic polymerization initiator, a photo radical polymerization initiator, a thermosetting agent, and a photosensitizer.

  The polymerizable liquid crystal composition of the present invention may contain a non-polymerizable liquid crystal compound having no polymerizable group. Examples of such non-polymerizable liquid crystal compounds are described in Licris, a database of liquid crystal compounds (LiqCryst, LCI Publisher GmbH, Hamburg, Germany). Such a polymerizable liquid crystal composition may further contain an additive such as a dichroic dye. In order to obtain a polymerizable liquid crystal composition with easy control of optical anisotropy and good coatability and to express the effect of the polymer of the present invention remarkably, non-polymerization in the polymerizable liquid crystal composition The content of the liquid crystalline compound is preferably 50% by weight or less, more preferably 30% by weight or less with respect to 100% by weight of the total amount of the compound (1) and other polymerizable compounds.

［式（Ａ）中、Ａ^４およびｎはそれぞれ前記式（Ｍ１）中のＡ^４およびｎと同義であり、Ｚ^Ａは独立して単結合または炭素数１〜１０のアルキレンであり、このアルキレンにおける任意の−ＣＨ_２−は−Ｏ−、−ＣＯ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＨ＝ＣＨ−、−ＣＦ＝ＣＦ−または−Ｃ≡Ｃ−で置き換えられてもよく、任意の水素はハロゲンで置き換えられてもよく、Ｒ^Ａは炭素数１〜１０のアルキル、炭素数２〜１０のアルケニル、炭素数１〜１０のアルコキシ、水素、塩素、フッ素、−ＣＮ、−ＣＦ_３または−ＯＣＦ_３である。］
以下に、具体例を示す。 Examples of non-polymerizable liquid crystal compounds include compounds represented by the following formula (A).

Wherein (A), ^{A 4} and n have the same meanings as ^{A 4} and n in the formula (M1) in, ^{Z A} is independently a single bond or alkylene having 1 to 10 carbon atoms, the alkylene Any —CH ₂ — in — may be replaced by —O—, —CO—, —COO—, —OCO—, —CH═CH—, —CF═CF— or —C≡C— Hydrogen may be replaced by halogen, and R ^A is alkyl having 1 to 10 carbons, alkenyl having 2 to 10 carbons, alkoxy having 1 to 10 carbons, hydrogen, chlorine, fluorine, —CN, —CF ₃ or -OCF _3. ]
A specific example is shown below.

  A non-liquid crystalline polymerizable compound can be added for the purpose of adjusting film forming properties, mechanical strength, and the like. Examples of preferable non-liquid crystal polymerizable compounds are (meth) acrylate compounds, vinyl compounds, styrene compounds, vinyl ether compounds, allyl ether compounds, epoxy compounds, and oxetane compounds.

  Preferred examples of the non-liquid crystalline polymerizable compound include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, phenyl (meth) acrylate, vinyl chloride, and vinyl fluoride. , Vinyl acetate, vinyl pivalate, vinyl 2,2-dimethylbutanoate, vinyl 2,2-dimethylpentanoate, vinyl 2-methyl-2-butanoate, vinyl propionate, vinyl stearate, 2-ethyl-2- Vinyl methylbutanoate, N-vinylacetamide, vinyl pt-butylbenzoate, vinyl N, N-dimethylaminobenzoate, vinyl benzoate, styrene, o-, m- or p-chloromethylstyrene, α-methylstyrene Tetrafluoroethylene, and hexafluoropropene, To, ethyl vinyl ether, hydroxybutyl monovinyl ether, t-amyl vinyl ether, cyclohexanedimethanol vinyl ether, hydroxybutyl allyl ether, glycerol monoallyl ether and allyl glycidyl ether. 3-ethyl-3-hydroxymethyloxetane, 3-methyl-3-hydroxymethyloxetane, di (1-ethyl (3-oxetanyl)) methyl ether, 3-ethyl for the purpose of adjusting the viscosity of the composition or reducing cure shrinkage -3- (2-ethylhexyloxymethyl) oxetane or the like may be added.

  In order to further increase the film-forming ability of the polymer, a polyfunctional acrylate can be added to the composition. Preferred polyfunctional acrylates are 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, 1,9-nonanediol diacrylate, neopentyl glycol diacrylate, triethylene glycol diacrylate, dipropylene glycol diacrylate , Tripropylene glycol diacrylate, tetraethylene glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane EO addition triacrylate, pentaerythritol triacrylate, trisacryloxyethyl phosphate, bisphenol A EO addition diacrylate, bisphenol A glycidyl Diacrylate (trade name: Biscoat 700, manufactured by Osaka Organic Chemical Co., Ltd.) and polyethylene glycol Diacrylate.

  In order to further increase the film-forming ability of the polymer, a compound having a polyfunctional cationic polymerization group can be added to the composition. As examples of preferred compounds, the following compounds (5-1) to (5-9) may also be mentioned. These compounds may be added to the polymerizable liquid crystal composition of the present invention to be used for adjusting the viscosity, adjusting the alignment, or increasing the hardness of the polymer.

In these compounds, Q ⁵ is independently alkylene having 2 to 20 carbon atoms, and any hydrogen in the alkylene may be replaced by fluorine or chlorine, and any —CH ₂ — is —O—, —COO—, —OCO—, —CH═CH— or —C≡C— may be substituted, and P ⁵ is independently any one of the above formulas (2-2) to (2-4). It is a group represented by one.

  Other examples of the polymerizable compound include an epoxy compound having one polymerizable group and an epoxy compound having two or more polymerizable groups. As epoxy compounds that may be added to the composition, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AD type epoxy resin, resorcin type epoxy resin, hydroquinone type epoxy resin, catechol type epoxy resin , Epoxy resins derived from dihydric phenols such as dihydroxynaphthalene type epoxy resin, biphenyl type epoxy resin, tetramethylbiphenyl type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, triphenylmethane type epoxy resin , Tetraphenylethane type epoxy resin, dicyclopentadiene-phenol modified epoxy resin, phenol aralkyl type epoxy resin, biphenyl aralkyl type epoxy Resin, naphthol novolac type epoxy resin, naphthol aralkyl type epoxy resin, naphthol-phenol co-condensed novolac type epoxy resin, naphthol-cresol co-condensed novolac type epoxy resin, aromatic hydrocarbon formaldehyde resin modified phenolic resin type epoxy resin, biphenyl modified novolak Epoxy resin derived from trihydric or higher phenols such as epoxy resin, tetrabromobisphenol A type epoxy resin, brominated phenol novolac type epoxy resin, polycarboxylic acid polyglycidyl ester, polyol polyglycidyl ether, fatty acid epoxy resin , Alicyclic epoxy resin, glycidylamine type epoxy resin, triphenolmethane type epoxy resin, dihydroxybenzene type epoxy resin, etc. , But it is not limited thereto. Moreover, these epoxy compounds may be used independently and may mix 2 or more types.

  Specific examples of the epoxy compound include alkyl monoglycidyl ethers having 2 to 25 carbon atoms (for example, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, decyl glycidyl ether, stearyl glycidyl ether), butanediol diglycidyl ether, 1, 6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, dodecanediol diglycidyl ether, pentaerythritol polyglycidyl ether, trimethylolpropane polyglycidyl ether, glycerol polyglycidyl ether, phenyl glycidyl ether, p-sec-butylphenyl glycidyl Ether, p-tert-butylphenyl glycidyl ether, resorching glycidyl ether, allyl glycidyl ether , Tetrafluoropropyl glycidyl ether, octafluoropropyl glycidyl ether, dodecafluoropentyl glycidyl ether, styrene oxide, 1,7-octadiene diepoxide, limonene diepoxide, limonene monooxide, α-pinene epoxide, β-pinene epoxide, cyclohexene Epoxide cyclooctene epoxide, vinylcyclohexene oxide, butoxypolyethylene glycol glycidyl ether, polyethylene glycol diglycidyl ether, 3,4-epoxycyclohexenylmethyl-3 ′, 4′-epoxycyclohexene carboxylate, 3,4-epoxycyclohexenylethyl- 3 ′, 4′-epoxycyclohexene carboxylate, 1,2-epoxy-4-vinylcyclohexane Vinylcyclohexene dioxide, allylcyclohexene dioxide, 1-epoxyethyl-3,4-epoxycyclohexane, 3,4-epoxy-4-methylcyclohexyl-2-propylene oxide, bis (3,4-epoxycyclohexyl) ether, Bis (3,4-epoxycyclohexylmethyl) adipate, diglycidyl phthalate, diglycidyl terephthalate, diglycidyl hexahydrophthalate, diglycidyl tetrahydrophthalate, tris (2,3-epoxypropyl) isocyanurate 3-ethyl-3-hydroxymethyloxetane, 3-ethyl-3- (phenoxymethyl) oxetane, di (1-ethyl (3-oxetanyl)) methyl ether, 3-ethyl-3-hydroxymethyl Kisetan, 3-methyl-3-hydroxymethyl oxetane, 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane. Furthermore, in addition to the above epoxy compounds, vinyl compounds such as ethyl vinyl ether, hydroxybutyl monovinyl ether, t-amyl vinyl ether, and cyclohexanedimethanol methyl vinyl ether can also be exemplified.

  Preferred examples of the nonionic surfactant include a fluorine-based nonionic surfactant, a silicone-based nonionic surfactant, and a hydrocarbon-based nonionic surfactant. Examples of fluorine-based nonionic surfactants are BYK-340, FT 251, 221 MH, FT 250, FTX-215M, FTX-218M, FTX-233M, FTX-245M, FTX-290M, FTX -209F, FTX-213F, Aftergent 222F, FTX-233F, FTX-245F, FTX-208G, FTX-218G, FTX-240G, FTX-206D, Aftergent 212D, FTX-218, FTX-220D, FTX-230D , FTX-240D, FTX-720C, FTX-740C, FTX-207S, FTX-211S, FTX-220S, FTX-230S, KB-L82, KB-L85, KB-L97, KB-L109, KB-L110, KB -F L, KB-F2M, KB-F2S, a KB-F3M, and KB-FaM.

  Examples of silicone-based nonionic surfactants are Polyflow ATF-2, Granol 100, Granol 115, Granol 400, Granol 410, Granol 435, Granol 440, Granol 450, Granol B-1484, Polyflow KL-250, Polyflow KL-260, Polyflow KL-270, Polyflow KL-280, BYK-300, BYK-302, BYK-306, BYK-307, BYK-310, BYK-315, BYK-320, BYK-322, BYK-323, BYK-325, BYK-330, BYK-331, BYK-333, BYK-337, BYK-341, BYK-344, BYK-345, BYK-346, BYK-347, BYK-348, BYK-370, BYK- 375, BY -377, BYK-378, BYK-3500, BYK-3510, and a BYK-3570. Examples of hydrocarbon-based nonionic surfactants include polyflow no. 3, Polyflow No. 50EHF, Polyflow No. 54N, Polyflow No. 75, Polyflow No. 77, Polyflow No. 85HF, Polyflow No. 90, polyflow no. 95, BYK-350, BYK-352, BYK-354, BYK-355, BYK-358N, BYK-361N, BYK-380N, BYK-381, BYK-392, and BYK-Silclean3700.

The above-mentioned polyflow and granol are both names of products sold by Kyoeisha Chemical Co., Ltd. BYK is the name of a product sold by Big Chemie Japan. Footent, FTX and KB are names of products sold by Neos Co., Ltd.
As the surfactant, other types of surfactants may be used as necessary. Specifically, polyether compounds, acrylic acid copolymer compounds, titanate compounds, imidazolines, quaternary ammonium salts, alkylamine oxides, polyamine derivatives, polyoxyethylene-polyoxypropylene condensates, polyethylene glycol and the like Esters, sodium lauryl sulfate, ammonium lauryl sulfate, amines of lauryl sulfate, alkyl-substituted aromatic sulfonates, alkyl phosphates, aliphatic or aromatic sulfonic acid formalin condensates, laurylamidopropyl betaine, laurylaminoacetic acid betaine, polyethylene glycol Various compounds such as fatty acid esters, polyoxyethylene alkylamine, perfluoroalkyl sulfonate, and perfluoroalkyl carboxylate can be used. These surfactants have effects such as facilitating application of the composition to a support substrate and the like.

  A cationic photopolymerization initiator may be added to the composition of the present invention. Examples of the photocationic polymerization initiator include diaryl iodonium salts (hereinafter abbreviated as DAS), triarylsulfonium salts (hereinafter abbreviated as TAS), and the like. DAS includes diphenyliodonium tetrafluoroborate, diphenyliodonium hexafluorophosphonate, diphenyliodonium hexafluoroarsenate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium trifluoroacetate, diphenyliodonium-p-toluenesulfonate, diphenyliodoniumtetra (pentafluorophenyl) ) Borate, 4-methoxyphenylphenyliodonium tetrafluoroborate, 4-methoxyphenylphenyliodonium hexafluorophosphonate, 4-methoxyphenylphenyliodonium hexafluoroarsenate, 4-methoxyphenylphenyliodonium trifluoromethanesulfonate, 4-methoxypheny Phenyliodonium trifluoroacetate, 4-methoxyphenylphenyliodonium-p-toluenesulfonate, 4-methoxyphenylphenyliodonium diphenyliodoniumtetra (pentafluorophenyl) borate, bis (4-tert-butylphenyl) iodoniumdiphenyliodoniumtetrafluoroborate Bis (4-tert-butylphenyl) iodonium diphenyliodonium hexafluoroarsenate, bis (4-tert-butylphenyl) iodonium diphenyliodonium trifluoromethanesulfonate, bis (4-tert-butylphenyl) iodonium trifluoroacetate, bis ( 4-tert-butylphenyl) iodonium p-toluenesulfonate, bis (4 tert- butylphenyl) iodonium diphenyl iodonium tetra (pentafluorophenyl) borate.

DAS can be made highly sensitive by adding a photosensitizer such as thioxanthone, phenothiazine, chlorothioxanthone, xanthone, anthracene, diphenylanthracene, and rubrene.

  TAS includes triphenylsulfonium tetrafluoroborate, triphenylsulfonium hexafluorophosphonate, triphenylsulfonium hexafluoroarsenate, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium trifluoroacetate, triphenylsulfonium-p-toluenesulfonate, Triphenylsulfonium tetra (pentafluorophenyl) borate, 4-methoxyphenyldiphenylsulfonium tetrafluoroborate, 4-methoxyphenyldiphenylsulfonium hexafluorophosphonate, 4-methoxyphenyldiphenylsulfonium hexafluoroarsenate, 4-methoxyphenyldiphenylsulfonium trifluoromethane Sulfonar 4-methoxyphenyldiphenylsulfonium trifluoroacetate, 4-methoxyphenyldiphenylsulfonium-p-toluenesulfonate, 4-methoxyphenyldiphenylsulfonium triphenylsulfonium tetra (pentafluorophenyl) borate, 4-phenylthiophenyldiphenylsulfonium tetrafluoroborate 4-phenylthiophenyldiphenylsulfonium hexafluorophosphonate, 4-phenylthiophenyldiphenylsulfonium hexafluoroarsenate, 4-phenylthiophenyldiphenylsulfonium trifluoromethanesulfonate, 4-phenylthiophenyldiphenylsulfonium-p-toluenesulfonate, 4 -Phenylthiophenyl diphenylsulfonium La (pentafluorophenyl) borate, and the like.

  Specific product names of the cationic photopolymerization initiator include UCC's products Cyracure UVI-6990, Cyracure UVI-6974 and Cyracure UVI-6922, and Adeka optomer SP-150, a product of Asahi Denka Kogyo Co., Ltd. , SP-152, SP-170 and SP-172, Rhodia's product PHOTOINITIATOR 2074, Ciba Specialty Chemicals 'product Irgacure 250, GE Silicones' product UV-9380C, Sun Apro Corp. In addition to HS series and CPI series of products, TPS series, TAZ series, DPI series, BPI series, MDS series, DTS series, SI series, PI series, NDI series, PAI series, NAI series from Midori Chemical Co., Ltd. NI Siri 'S, DAM series, MBZ series, PYR series, DNB series, mention may be made of the NB series and the like.

  The composition of the present invention can be combined with a photocationic polymerization initiator and hybrid-cured by adding a photoradical polymerization initiator. Examples of radical photopolymerization initiators include Darocur 1173 (2-hydroxy-2-methyl-1-phenylpropan-1-one) and Irgacure 184 (1) from the products of Ciba Specialty Chemicals. -Hydroxycyclohexyl phenyl ketone), Irgacure 651 (2,2-dimethoxy-1,2-diphenylethane-1-one), Irgacure 500, Irgacure 2959, Irgacure 907, Irgacure 369, Irgacure 1300, Irgacure Cure 819, Irgacure 1700, Irgacure 1800, Irgacure 1850, Darocur 4265, and Irgacure 784.

Other examples of photo radical polymerization initiators include p-methoxyphenyl-2,4-bis (trichloromethyl) triazine, 2- (p-butoxystyryl) -5-trichloromethyl-1,3,4-oxadiazole 9-phenylacridine, 9,10-benzphenazine, benzophenone / Michler's ketone mixture, hexaarylbiimidazole / mercaptobenzimidazole mixture, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, Benzyldimethyl ketal, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2,4-diethylxanthone / methyl p-dimethylaminobenzoate, benzophenone / methyltriethanolamine It is a mixture.
In the present invention, a thermal polymerization initiator may be added. Specific examples of product names are San-Aid (main agent) of products of Sanshin Chemical Industry Co., Ltd. SI-60, SI-80, SI-100, SI-110, SI-145, SI-150, SI-160 SI-180, and sun aid (auxiliary) SI. These may be used together with a photo radical initiator and a photo cationic polymerization initiator, or may be used together with a photo radical initiator.

  The polymerizable liquid crystal composition of the present invention may contain a thermosetting agent. Examples of the thermosetting agent include acidic or basic compounds having an amino group, carboxyl group, mercapto group, etc., compounds having a phenol moiety or compounds having an acid anhydride moiety. More preferable are a basic compound having an amino group, a compound having a phenol, and a compound having an acid anhydride. These may be used together with a photocationic polymerization initiator or a photoradical initiator.

  Examples of thermosetting agents having amino groups are diethylenetriamine, triethylenetetramine, tetraethylenepentamine, m-xylenediamine, trimethylhexamethylenediamine, 2-methylpentamethylenediamine, diethylaminopropylamine, isophoronediamine, 1,3 -Bisaminomethylcyclohexane, bis (4-aminocyclohexyl) methane, norbornenediamine, 1,2-diaminocyclohexane, laromine, diaminodiphenylmethane, metaphenylenediamine, diaminodiphenylsulfone, polyoxypropylenediamine, polyoxypropylenetriamine, polycyclohexyl Polyamine mixture, N-aminoethylpiperazine.

  Examples of the thermosetting agent having a phenol group are phenol novolak, xylylene novolak, bisphenol A novolak, triphenylmethane novolak, biphenyl novolak, dicyclopentadiene phenol novolak, and terpene phenol novolak.

  Examples of thermosetting agents with acid anhydrides include tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyl nadic anhydride, hydrogenated methyl nadic anhydride, Alkyltetrahydrophthalic anhydride, methylcyclohexenetetracarboxylic dianhydride, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic dianhydride, ethylene glycol bisanhydro trimellitate, glycerin bis (an Hydrotrimellitate) monoacetate, dodecenyl succinic anhydride, aliphatic dibasic acid polyanhydride, chlorendic anhydride.

ここに、Ｒ^Ｚは独立して炭素数１〜１０の直鎖状のアルキルである。 The polymerizable liquid crystal composition of the present invention may contain a photosensitizer. Examples of the photosensitizer are a thioxanthone derivative, an anthraquinone derivative, and a naphthoquinone derivative, and preferred examples are the following compounds (Z-1) to (Z-6). Particularly preferred photosensitizers are the compound (Z-1) and the compound (Z-2). A photosensitizer may be used by 1 type, or 2 or more types may be mixed and used for it.

Here, R ^Z is independently a linear alkyl having 1 to 10 carbon atoms.

A compound in which R ^Z is n-butyl in the compound (Z-1) can be obtained as ANTHRACURE UVS-1331 from Kawasaki Chemical Industry Co., Ltd. The compound (Z-2) can be obtained as ANTHRACURE ET-2111 of Kawasaki Kasei Kogyo Co., Ltd. Compound (Z-3) is available as Speedcure CTX from Lambson. Compound (Z-4) is available as Quantacure ITX from Shell Chemical Co., Ltd. Compound (Z-5) is available as Kayacure Detx-S from Nippon Kayaku Co., Ltd. Compound (Z-6) is available as Lambson Speedcure CPTX.

  By using a combination of DAS and a photosensitizer, sensitivity to light is improved. A preferable mixing ratio of DAS and photosensitizer is 10 to 200 parts by weight of photosensitizer with respect to 100 parts by weight of DAS. A more preferable mixing ratio is 20 to 100 parts by weight of the photosensitizer with respect to 100 parts by weight of DAS. In order to further improve the weather resistance of the polymerizable liquid crystal composition, an ultraviolet absorber, a light stabilizer (radical scavenger), an antioxidant and the like may be added. Examples of UV absorbers are Tinuvin PS, Tinuvin P, Tinuvin 99-2, Tinuvin 109, Tinuvin 213, Tinuvin 234, Tinuvin 326, Tinuvin 328, Tinuvin 329, Tinuvin 384-2, Tinuvin 571, Tinuvin 900, Tinuvin 928, Tinuvin 1130, Tinuvin 400, Tinuvin 405, Tinuvin 460, Tinuvin 479, Tinuvin 5236, Adekastab LA-32, Adekastab LA-34, Adekastab LA-36, Adekastab LA-31, Adekastab 1413, and Adekastab LA-51. “Tinubin” is a trade name of Ciba Specialty Chemicals, and “Adeka Stub” is a trade name of Asahi Denka Co., Ltd.

  Examples of light stabilizers are Tinuvin 111FDL, Tinuvin 123, Tinuvin 144, Tinuvin 152, Tinuvin 292, Tinuvin 622, Tinuvin 770, Tinuvin 765, Tinuvin 780, Tinuvin 905, Tinuvin 5100, Tinuvin 5050, 5060, Tinuvin 5151, Chimassorb 119FL , Kimabsorb 944FL, Kimabsorb 944LD, ADK STAB LA-52, ADK STAB LA-57, ADK STAB LA-62, ADK STAB LA-67, ADK STAB LA-63P, ADK STAB LA-68LD, ADK STAB LA-77, ADK STAB LA-82, ADK STAB LA- 87, Siasorb UV-3346 manufactured by Cytec, and Goodlight UV-3034 manufactured by Goodrich. “Kimasorb” is a trade name of Ciba Specialty Chemicals.

  Examples of antioxidants are ADK STAB AO-20, AO-30, AO-40, AO-50, AO-60, AO-80, manufactured by Asahi Denka Co., Ltd., Sumilizer BHT sold by Sumitomo Chemical Co., Ltd. Sumilizer BBM-S, Sumilizer GA-80, and Irganox 1076, Irganox 1010, Irganox 3114, and Irganox 245 sold by Ciba Specialty Chemicals. You may use these commercial items.

  The composition of the present invention can also be cured by utilizing a base proliferation reaction by light (K. Arimitsu, M. Miyamoto, K. Ichimura, Angew. Chem. Int. Ed, 2000, 39, 3425).

  The polymerizable liquid crystal composition of the present invention may contain a solvent as described above. Usually, the polymerizable liquid crystal composition is prepared by dissolving the components described above in a solvent. In order to facilitate coating, the polymerizable liquid crystal composition may be further diluted with a solvent to adjust the viscosity of the polymerizable liquid crystal composition. Solvents can be used alone or in admixture of two or more. Examples of solvents are ester solvents, amide solvents, alcohol solvents, ether solvents, glycol monoalkyl ether solvents, aromatic hydrocarbon solvents, halogenated aromatic hydrocarbon solvents, aliphatic hydrocarbon solvents, Halogenated aliphatic hydrocarbon solvents and alicyclic hydrocarbon solvents, ketone solvents, and acetate solvents.

  Preferred examples of the ester solvent include alkyl acetate (eg, methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, 3-methoxybutyl acetate, isobutyl acetate, pentyl acetate and isopentyl acetate), ethyl trifluoroacetate, propion Alkyl (eg, methyl propionate, methyl 3-methoxypropionate, ethyl propionate, propyl propionate and butyl propionate), alkyl butyrate (eg: methyl butyrate, ethyl butyrate, butyl butyrate, isobutyl butyrate and propyl butyrate), Dialkyl malonate (eg diethyl malonate), alkyl glycolate (eg methyl glycolate and ethyl glycolate), alkyl lactate (eg methyl lactate, ethyl lactate, isopropyl lactate, n-propyl lactate, butyl lactate and lactic acid) Ethylhexyl), monoacetin, a γ- butyrolactone and γ- valerolactone.

  Preferred examples of the amide solvent include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N-methylpropionamide, N, N-dimethylformamide, N, N-diethylformamide, N, N-diethylacetamide, N, N-dimethylacetamide dimethyl acetal, N-methylcaprolactam and dimethylimidazolidinone.

  Preferred examples of the alcohol solvent include methanol, ethanol, 1-propanol, 2-propanol, 1-methoxy-2-propanol, t-butyl alcohol, sec-butyl alcohol, butanol, 2-ethylbutanol, n-hexanol, n -Heptanol, n-octanol, 1-dodecanol, ethylhexanol, 3,5,5-trimethylhexanol, n-amyl alcohol, hexafluoro-2-propanol, glycerin, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, Propylene glycol, dipropylene glycol, tripropylene glycol, hexylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,5 Pentanediol, 2,4-pentanediol, 2,5-hexanediol, 3-methyl-3-methoxybutanol, cyclohexanol and methylcyclohexanol.

  Preferred examples of the ether solvent are ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, bis (2-propyl) ether, 1,4-dioxane and tetrahydrofuran (THF).

  Preferred examples of the glycol monoalkyl ether solvent include ethylene glycol monoalkyl ether (eg, ethylene glycol monomethyl ether and ethylene glycol monobutyl ether), diethylene glycol monoalkyl ether (eg, diethylene glycol monoethyl ether), triethylene glycol monoalkyl ether, Propylene glycol monoalkyl ether (eg: propylene glycol monobutyl ether), dipropylene glycol monoalkyl ether (eg: dipropylene glycol monomethyl ether), ethylene glycol monoalkyl ether acetate (eg: ethylene glycol monobutyl ether acetate), diethylene glycol monoalkyl ether Acetate (eg, diethylene glycol) Monoethyl ether acetate), triethylene glycol monoalkyl ether acetate, propylene glycol monoalkyl ether acetate (eg, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate and propylene glycol monobutyl ether acetate), dipropylene glycol monoalkyl ether acetate (Example: dipropylene glycol monomethyl ether acetate) and diethylene glycol methyl ethyl ether.

  Preferred examples of the aromatic hydrocarbon solvent include benzene, toluene, xylene, mesitylene, ethylbenzene, diethylbenzene, i-propylbenzene, n-propylbenzene, t-butylbenzene, s-butylbenzene, n-butylbenzene, and tetralin. It is. A preferred example of the halogenated aromatic hydrocarbon solvent is chlorobenzene. Preferred examples of the aliphatic hydrocarbon solvent are hexane and heptane. Preferred examples of the halogenated aliphatic hydrocarbon solvent are chloroform, dichloromethane, carbon tetrachloride, dichloroethane, trichloroethylene and tetrachloroethylene. Preferred examples of the alicyclic hydrocarbon solvent are cyclohexane and decalin.

  Preferred examples of the ketone solvent are acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, cyclopentanone, and methyl propyl ketone.

  Preferred examples of the acetate solvent are ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monoethyl ether acetate, methyl acetoacetate, and 1-methoxy-2-propyl acetate. Among these solvents, it is very important that the solubility in highly safe organic solvents is high. Examples of this solvent are ethyl lactate, ethyl pyruvate, 2-heptanone, butyl acetate, methyl 3-methoxypropionate, methyl 3-ethoxypropionate, and propylene glycol monoethyl ether acetate.

  From the viewpoint of the solubility of the polymerizable liquid crystal compound, it is preferable to use an amide solvent, an aromatic hydrocarbon solvent, or a ketone solvent. In view of the boiling point of the solvent, an ester solvent, an alcohol solvent, an ether solvent, a glycol monomer. Alkyl ether solvents are preferred. Although there is no particular limitation regarding the selection of the solvent, when a plastic substrate is used as the supporting base, it is necessary to lower the drying temperature in order to prevent deformation of the substrate and to prevent the solvent from attacking the substrate. Examples of solvents preferably used in such cases are aromatic hydrocarbon solvents, ketone solvents, ester solvents, ether solvents, alcohol solvents, acetate solvents, and glycol monoalkyl ether solvents. Of these solvents, it is very important that the solubility in highly safe organic solvents is high. Examples of highly safe organic solvents are ethyl lactate, ethyl pyruvate, 2-heptanone, butyl acetate, methyl 3-methoxypropionate, methyl 3-ethoxypropionate, and propylene glycol monoethyl ether acetate.

  The proportion of the solvent in the polymerizable liquid crystal composition of the present invention is 0 to 95% by weight. However, considering the compatibility of the polymerizable liquid crystal compound and the optimum viscosity when applying this solution, the solvent cost and the solvent are further reduced. Considering an economic point of view such as time and amount of heat during evaporation, it is preferably 40 to 95% by weight. A more preferable ratio is 45 to 90%, and a further preferable ratio is 50 to 85%.

  In the polymerizable liquid crystal composition of the present invention, factors that determine the alignment of liquid crystal molecules are 1) the type of compound contained in the composition, 2) the type of support substrate, and 3) the method of alignment treatment. A preferred orientation treatment method is a method such as oblique vapor deposition of silicon oxide or etching into a slit shape. A particularly preferred orientation treatment method is rubbing in one direction with a rayon cloth or the like. In the rubbing process, the support substrate may be directly rubbed. The support substrate may be coated with a thin film such as polyimide or polyvinyl alcohol, and the thin film may be rubbed. Special thin films that give good orientation without rubbing are also known. Alternatively, the support substrate may be coated with a side chain type liquid crystal polymer.

  The alignment of the liquid crystal molecules includes homogenous (parallel), homeotropic (vertical), and hybrid. Homogeneous means a state in which the orientation vector is parallel to the substrate and in one direction. Homeotropic means a state in which the orientation vector is perpendicular to the substrate. Hybrid refers to a state where the orientation vector rises from parallel to vertical as it moves away from the substrate. These orientations are observed in a composition having a nematic phase or the like.

By fixing the alignment state of the liquid crystal molecules, films having various optical properties can be obtained. Z-axis the film in the thickness direction takes x and y axes in the orthogonal direction on the film plane, the x-axis direction, y-axis direction, the refractive index of the z-axis direction n _x, n _y, and n _z Optical anisotropy can be expressed as a refractive index ellipsoid representing a three-dimensional refractive index. Polymer having a homogeneous orientation is in the direction n _x direction of the optical axis, since the optical axis of the refractive index is larger than the refractive index in the direction thereof orthogonal, the relationship between the three-dimensional refractive index n _x> n _y = It is classified into A plate that can be expressed as _nz . A polymer having homeotropic orientation has the optical axis direction in the _nz direction, and the refractive index in the optical axis direction is larger than the refractive index in the orthogonal direction, so that the relationship of the three-dimensional refractive index is expressed as _nx = _ny. It is classified into C plates that can be expressed as < _nz . A polymer having a hybrid orientation has the optical properties of an O-plate. For example, the present invention can be applied to a viewing angle compensator in a TN (Twisted Nematic) mode element.

  The polymerizable liquid crystal composition of the present invention may contain an optically active compound. A composition obtained by adding an appropriate amount of an optically active compound is applied onto a substrate subjected to orientation treatment and polymerized to obtain a retardation plate having a helical structure (twisted structure). This helical structure is fixed by the polymerization of the compound (1). The properties of the obtained molded article having optical anisotropy depend on the helical pitch of the helical structure. The helical pitch length can be adjusted by the type and amount of the optically active compound. One optically active compound may be added, but a plurality of optically active compounds may be used for the purpose of offsetting the temperature dependence of the helical pitch.

  The selective reflection of visible light, which is a characteristic of a molded article having optical anisotropy as described above, is that a helical structure acts on incident light and reflects circularly polarized light or elliptically polarized light. The selective reflection characteristic is expressed by λ = n · Pitch (λ is a selective reflection center wavelength, n is an average refractive index of a molded article having optical anisotropy, and Pitch is a helical pitch). The band (Δλ) can be adjusted as appropriate. If the pitch of the helix is 1 / n of the wavelength of the light, either the left or right circularly polarized light can be selectively reflected according to Bragg's law according to the direction of the helix in the light having that wavelength. This can be used, for example, as a circularly polarized light separating functional element. The direction of the helix depends on the configuration of the optically active compound. A desired helical direction can be induced by appropriately selecting the configuration of the optical compound. For example, according to the method disclosed in JP-A-6-281814, a molded body in which the helical pitch continuously changes in the thickness direction of the molded body having optical anisotropy is obtained, and a wavelength region corresponding to the pitch is obtained. It can reflect light. In order to improve the color purity, Δλ should be reduced, and Δλ should be increased when broadband reflection is desired. Further, this selective reflection is greatly affected by the cell thickness. In order to maintain color purity, the cell thickness must be kept from becoming too small. In order to maintain the uniformity of orientation, the cell thickness must not be too large. Accordingly, it is necessary to adjust the cell thickness appropriately, and 0.5 to 25 μm is preferable, and 0.5 to 5 μm is more preferable.

  By making the helical pitch shorter than visible light, a negative C plate (C-plate) described in W. H. de Jeu, Physical Properties of Liquid Crystalline Materials, Gordon and Breach, New York (1980) can be prepared. In order to shorten the helical pitch, it can be achieved by using an optically active compound having a large twisting force (HTP: helical twisting power) and further increasing the amount of addition. Specifically, a negative C plate can be prepared by setting λ to 350 nm or less, preferably 200 nm or less. This negative type C plate is an optical compensation film suitable for VAN type, VAC type, OCB type and the like among liquid crystal display elements.

さらに上記光学活性化合物の中でも、ねじり力（ＨＴＰ：ヘリカル・ツイスティング・パワー）が大きいものは、らせんピッチを短くする上では好適である。ねじり力の大きな化合物の代表例が、ＧＢ２２９８２０２号公報、ＤＥ１０２２１７５１号公報で開示されている。 Any optically active compound may be used as long as it induces a helical structure and can be appropriately mixed with the polymerizable liquid crystal composition as a base. In addition, either a polymerizable compound or a non-polymerizable compound may be used, and an optimum compound can be added according to the purpose. In consideration of heat resistance and solvent resistance, a polymerizable compound is more preferable. Examples of the skeleton that exhibits optical activity include alkylene having one or more asymmetric carbons, alkenylene, and those having the following partial structures.

Further, among the optically active compounds, those having a large twisting force (HTP: helical twisting power) are suitable for shortening the helical pitch. Representative examples of compounds having a large torsional force are disclosed in GB2298202 and DE10221751.

The more preferable example of the polymeric compound which has optical activity below is given. However, it is not limited to this.

In these compounds, Q ⁶ is independently alkylene having 1 to 20 carbons, and any hydrogen in the alkylene may be replaced by fluorine, and any —CH ₂ — may be —O— or —COO. -, -OCO-, -CH = CH-, or -C≡C- may be substituted, and P ⁶ is independently any one of the above formulas (2-2) to (2-4). It is group represented by these.

  Next, the polymerization conditions of the composition of the present invention will be described. A polymer is obtained by polymerizing the polymerizable liquid crystal composition of the present invention. When a polymer having an excellent orientation is obtained, polymerization using a photopolymerization catalyst is preferable to thermal polymerization. This is because it is easy to perform polymerization under the condition that the composition is liquid crystal.

Preferred types of light used for photopolymerization include ultraviolet light, visible light, infrared light, and the like. Electromagnetic waves such as electron beams and X-rays may be used. Usually, ultraviolet rays or visible rays are preferable. A preferable wavelength range is 150 to 500 nm. A more preferable range is 250 to 450 nm, and a most preferable range is 300 to 400 nm. The light source is a low-pressure mercury lamp (sterilization lamp, fluorescent chemical lamp, black light), high-pressure discharge lamp (high-pressure mercury lamp, metal halide lamp), short arc discharge lamp (ultra-high pressure mercury lamp, xenon lamp, mercury xenon lamp), etc. . A preferred light source is an ultra high pressure mercury lamp. You may irradiate the composition with the light from a light source as it is. The composition may be irradiated with a specific wavelength (or a specific wavelength region) selected by a filter. A preferable irradiation energy density is ² to 5000 mJ / cm ² . A more preferable range is 10 to 3000 mJ / cm ² . A particularly preferable range is 100 to 2000 mJ / cm ² . A preferable illuminance is 0.1 to 5000 mW / cm ² . Further preferable illuminance is 1 to 2000 mW / cm ² . The temperature at which light is irradiated is set so that the composition has a liquid crystal phase. A preferable irradiation temperature is 100 ° C. or less. Since polymerization by heat can occur at a temperature of 100 ° C. or higher, there are cases where good orientation cannot be obtained.

Next, the polymer of the present invention will be described.
A polymer is obtained by polymerizing the compound (1). When only one of the compounds (1) is polymerized, a homopolymer is obtained. This polymer consists of one structural unit. When a composition containing at least two compounds (1) is polymerized, a copolymer is obtained. This copolymer has at least two structural units. For the production of a film having optical anisotropy, which is the object of the present invention, polymerization in an aligned liquid crystal state is desirable, and thus the photocationic polymerization method is a particularly preferable polymerization method. The polymer obtained by polymerizing the compound (1) is colorless and transparent, has low photoelasticity, is difficult to peel from the support substrate, has sufficient hardness, has high heat resistance, and has high weather resistance. A plurality of characteristics are satisfied among the characteristics such as.

  The uses of this polymer are as follows. This polymer can be used as a molded product having optical anisotropy. Examples of the use of this polymer are optical films such as retardation plates (1/2 wavelength plates, 1/4 wavelength plates, etc.), antireflection films, selective reflection films, and viewing angle compensation films. Polymers having orientation such as homogeneous, hybrid, homeotropic and twist can be used for retardation plates, polarizing elements, liquid crystal alignment films, antireflection films, selective reflection films, viewing angle compensation films, and the like. Such a polymer is used for the purpose of optical compensation in a phase difference plate of a liquid crystal display element, a viewing angle compensation film, and the like. An example of an important industrial application is viewing angle compensation in liquid crystal display elements such as VA mode, IPS mode, TN mode, and MVA mode.

Applications of this polymer include the following.
This polymer can be used in high thermal conductive epoxy resins, adhesives, synthetic polymers with anisotropy in mechanical properties such as strength, elastic modulus, and elongation, cosmetics, decorative products, nonlinear optical materials and information storage materials. Can also be used. Thermoplastic resins can be used for these applications. This thermoplastic resin is a linear polymer that is not branched, and is obtained by polymerizing the liquid crystal composition of the present invention mainly composed of a monofunctional compound. These weight average molecular weights are 500-1,000,000, Preferably it is 1,000-500,000, More preferably, it is 5,000-100,000.

  A phase difference plate, which is an example of a use of a polymer, has a function of converting a polarization state. The half-wave function plate has a function of rotating the vibration direction of linearly polarized light by 90 degrees. The composition is applied onto the support substrate so as to satisfy the formula d = λ / 2 × Δn. Here, d is the thickness of the composition, λ is the wavelength, and Δn is the optical anisotropy. After the composition is oriented, it is photopolymerized to obtain a half-wavelength functional plate. On the other hand, the 1/4 wavelength functional plate has a function of converting linearly polarized light into circularly polarized light or converting circularly polarized light into linearly polarized light. In this case, a coating film of the composition may be prepared so as to satisfy the condition of d = λ / 4 × Δn. The thickness (d) of the polymer is adjusted as follows. In the method of applying the composition on a support substrate after diluting the composition with a solvent, a coating film having a desired thickness can be obtained by appropriately selecting the concentration of the composition, the application method, the application conditions, and the like. Can do. A method using a liquid crystal cell is also preferable. The liquid crystal cell is convenient because it has an alignment film such as polyimide. When injecting the composition into the liquid crystal cell, the thickness of the coating film can be adjusted by the interval of the liquid crystal cell.

  By combining photopolymerization and thermal polymerization, a patterned retardation plate can also be provided. A polymerizable liquid crystal composition is applied on a support substrate, aligned, and then irradiated with light through a photomask to photopolymerize only the irradiated portion. Next, by heating the polymer, the uncured part causes a decrease in or lack of optical anisotropy due to disorder of orientation and transition to an isotropic phase. A patterned retardation plate can be prepared by thermally polymerizing an uncured portion.

  The shape of the polymer is a film, plate, grain, powder or the like. The polymer may be molded. To obtain a film polymer, a support substrate is generally used. A film is obtained by applying the composition on a support substrate and polymerizing a paint film having a liquid crystal phase. The preferred polymer thickness depends on the value of the optical anisotropy of the polymer and the application. The preferred thickness of the polymer is in the range of 0.05 to 50 μm. A more preferable thickness is in the range of 0.1 to 20 μm. A particularly preferred thickness is in the range of 0.5 to 10 μm. The haze value (haze value) of these polymers is generally 1.5% or less. The transmittance of these polymers is generally 80% or more in the visible light region. Such a polymer is suitable as an optically anisotropic thin film used for a liquid crystal display element.

  Examples of the support substrate are triacetyl cellulose (sometimes referred to as TAC), polyvinyl alcohol, polyimide, polyester, polyarylate, polyetherimide, polyethylene terephthalate, and polyethylene naphthalate. Examples of product names are “Arton” from JSR Corporation, “Zeonex” and “Zeonoa” from Nippon Zeon Corporation, and “Apel” from Mitsui Chemicals, Inc. The support substrate is a uniaxially stretched film, a biaxially stretched film, or the like. A preferred support substrate is a triacetyl cellulose film. You may use this film as it is, without pre-processing. This film may be subjected to a surface treatment such as a saponification treatment, a corona discharge treatment, a UV-ozone treatment, or a plasma treatment, if necessary. Other examples include a support substrate made of metal such as aluminum, iron and copper, and a support substrate made of glass such as alkali glass, borosilicate glass and flint glass.

  The coating film on the support substrate is prepared by applying the composition as it is. The coating film can also be prepared by dissolving the composition in a suitable solvent and applying it, and then removing the solvent. Examples of the coating method include spin coating, roll coating, curtain coating, flow coating, printing, micro gravure coating, gravure coating, wire bar coating, dip coating, spray coating, meniscus coating, and cast film formation.

  The present invention will be described in more detail by way of examples, but the present invention is not limited by the following examples. The structure of the compound was confirmed by nuclear magnetic resonance spectrum, infrared absorption spectrum, mass spectrum and the like. The unit of the phase transition temperature is ° C., C represents a crystal, and I represents an isotropic liquid phase. The parentheses indicate a monotropic liquid crystal phase. In the examples, the liter, which is a unit of capacity, is represented by the symbol L. The physical property value measurement method is shown below.

<Confirmation of compound structure>
The structure of the synthesized compound was confirmed by measurement of proton NMR (Bruker: DRX-500) at 500 MHz. The described numerical value represents ppm, s represents a singlet, d represents a doublet, t represents a triplet, and m represents a multiplet.

<Phase transition temperature>
A sample was placed on a hot plate of a melting point measuring apparatus equipped with a polarizing microscope, and the temperature was raised at a rate of 3 ° C./min. The temperature at which the liquid crystal phase transitions to another liquid crystal phase was measured. C is a crystal, N is a nematic phase, and I is an isotropic liquid. The clearing point (NI point) is the upper limit temperature of the nematic phase or the transition temperature from the nematic phase to the isotropic liquid. “C 50 N 63 I” indicates that the crystal transitioned to a nematic phase at 50 ° C. and the nematic phase to an isotropic liquid at 63 ° C.

<Alignment of liquid crystal molecules>
A polymer film (liquid crystal alignment film) was prepared on a glass substrate with a rubbed polyimide alignment film. The orientation of the polymer was determined visually by the following method based on the angle dependence of the transmitted light intensity.
(1) Observation method by visual observation A polymer film was sandwiched between two polarizing plates arranged in crossed Nicols, and light was irradiated from the direction perpendicular to the film surface (the tilt angle was 0 degree). The change in transmitted light was observed while increasing the tilt angle of irradiation from 0 degrees to, for example, 50 degrees. The direction of tilting the irradiation was matched with the rubbing direction (long axis direction of liquid crystal molecules). The orientation was judged to be homogeneous when the transmitted light from the vertical direction was maximal. In homogeneous alignment, the alignment vector of liquid crystal molecules is parallel to the glass substrate, and this polymer film functions as an A-plate. On the other hand, when the transmitted light from the vertical direction is the smallest and the transmitted light increases as the tilt angle increases, the orientation is judged to be homeotropic. This is because in homeotropic alignment, the alignment vector of liquid crystal molecules is perpendicular to the glass substrate, and this polymer film functions as a C-plate.
(2) Measurement by ellipsometer An OPTIPRO ellipsometer manufactured by Shintech Co., Ltd. was used. The polymer film was irradiated with light having a wavelength of 550 nm. The retardation (Δn × d) was measured while decreasing the incident angle of this light from 90 degrees with respect to the film surface.

<Photocationic polymerization>
The heat of polymerization by cationic photopolymerization was measured at 25 ° C. under a stream of dry air by irradiating the sample on the aluminum pan with ultraviolet rays using a photochemical reaction calorimeter PDC121 (Seiko Instruments Inc.).

<Synthesis of Compound (1-1-20)>
(First stage)
Under a nitrogen atmosphere, sodium hydroxide (11.1 g) is added to a mixture of toluene (30 ml) and water (30 ml), and the mixture is stirred at room temperature. Cyclohexene methanol (6.2 g), 1,4-dibromobutane (18.0 g), and tetrabutylammonium bromide (1.8 g) were added, and the mixture was stirred with heating under reflux for 3 hours. The organic layer was separated, and the resulting organic layer was washed successively with saturated aqueous sodium hydrogen carbonate and 10% brine, and dried over anhydrous magnesium sulfate. The residue obtained by evaporating the solvent under reduced pressure was purified by column chromatography (silica gel, eluent: toluene) to obtain a colorless liquid [H1] (5.9 g).

The NMR analysis value of compound [H1] is shown.
¹ H-NMR (CDCl ₃ ; δ ppm): 5.67 (s, 2H), 3.47-3.42 (m, 4H), 3.33-3.25 (m, 2H), 2.15 2.02 (m, 3H), 2.00-1.68 (m, 7H), 1.32-1.22 (m, 1H).

(Second stage)
Under a nitrogen atmosphere, a mixture of compound [H1] (5.9 g), 4-hydroxybenzoic acid methyl ester (4.0 g), potassium hydroxide (1.5 g), and DMF (60 ml) was heated at 80 ° C. for 6 hours. Stir. The precipitated salt was removed by vacuum filtration. Toluene (100 ml) and water (100 ml) were added to the filtrate, and the organic layer was separated. The obtained organic layer was washed successively with saturated aqueous sodium hydrogen carbonate and water, and the solvent was evaporated under reduced pressure. Next, methanol (20 ml), water (20 ml) and potassium hydroxide (1.5 g) were added to the residue, and the mixture was stirred for 3 hours with heating under reflux. The solvent was distilled off under reduced pressure, 3N aqueous hydrochloric acid (100 ml) and toluene (100 ml) were added, and the organic layer was separated. The obtained organic layer was washed with water, and the solvent was distilled off under reduced pressure. Purification by recrystallization (ethanol) gave colorless crystal compound [H2] (2.6 g).

The NMR analysis value of compound [H2] is shown.
¹ H-NMR (CDCl ₃ ; δ ppm): 8.05 (d, 2H), 6.93 (d, 2H), 5.67 (s, 2H), 4.07 (t, 2H), 3.50 (T, 2H), 3.35-3.27 (m, 2H), 2.15-2.03 (m, 3H), 1.95-1.68 (m, 7H), 1.33-1 .23 (m, 1H).

(5th stage)
In a nitrogen atmosphere, while cooling to a mixture of compound [H2] (2.6 g), methylhydroquinone (0.5 g), DMAP (4-dimethylaminopyridine) (0.2 g), dichloromethane (30 ml), DCC (1, 3-Dicyclohexylcarbodiimide) (1.9 g) was added and stirred at room temperature for 16 hours. The precipitated insoluble matter was removed by filtration under reduced pressure, water was added to the filtrate to separate the organic layer, and the obtained organic layer was washed successively with 2N hydrochloric acid and water, and dried over anhydrous magnesium sulfate. The residue obtained by distilling off the solvent under reduced pressure was subjected to column chromatography (silica gel, eluent: toluene-ethyl acetate mixture (volume ratio: toluene / ethyl acetate = 8/1)), and recrystallization (toluene-methanol mixture ( (Volume ratio: Toluene / methanol = 1/10)) to obtain colorless crystal compound [H3] (2.3 g).

The phase transition temperature and NMR analysis value of compound [H3] are shown.
C 72 N 98 I.I.
¹ H-NMR (CDCl ₃ ; δ ppm): 8.16 (d, 2H), 8.14 (d, 2H), 7.17 (d, 1H), 7.13 (d, 1H), 7.10 -7.06 (m, 1H), 6.99 (d, 2H), 6.97 (d, 2H), 5.68 (s, 2H), 4.12-4.07 (m, 4H), 3.51 (t, 4H), 3.36-3.29 (m, 4H), 2.25 (s, 3H), 2.15-2.02 (m, 6H), 1.96-1. 70 (m, 16H), 1.34-1.24 (m, 2H).

(Final stage: Synthesis of compound (1-1-20))
Under a nitrogen atmosphere, m-chloroperbenzoic acid (1.9 g) was added to a mixture of compound [H3] (2.3 g) and dichloromethane (25 ml) while cooling, and the mixture was stirred at room temperature for 16 hours. The precipitated insoluble matter was removed by filtration under reduced pressure, and the filtrate was washed successively with 10% aqueous sodium bisulfite, 3% aqueous sodium hydroxide and water, and dried over anhydrous magnesium sulfate. The residue obtained by distilling off the solvent under reduced pressure was subjected to column chromatography (silica gel, eluent: toluene-ethyl acetate mixture (volume ratio: toluene / ethyl acetate = 4/1)) and recrystallization (toluene-methanol mixture ( (Volume ratio: Toluene / methanol = 1/10)) to give colorless crystal compound (1-1-20) (0.9 g).

The phase transition temperature and NMR analysis value of a compound (1-1-20) are shown.
C62N85I.
¹ H-NMR (CDCl ₃ ; δ ppm): 8.18 (d, 2H), 8.14 (d, 2H), 7.18 (d, 1H), 7.13 (d, 1H), 7.10 -7.06 (m, 1H), 6.99 (d, 2H), 6.97 (d, 2H), 3.47 (t, 4H), 3.28-3.13 (m, 8H), 2.25 (s, 3H), 2.20-1.97 (m, 4H), 1.94-1.70 (m, 10H), 1.62-1.40 (m, 10H), 1. 20-1.10 (m, 1H), 1.06-0.96 (m, 1H).

<Synthesis of Compound (1-3-21)>
(First stage)
To a mixture of cyclohexene methanol (20.0 g), pyridine (20 ml) and toluene (60 ml), p-toluenesulfonic acid chloride (37.4 g) was added at room temperature, and the mixture was stirred at room temperature for 16 hours. The precipitated insoluble matter was removed by filtration under reduced pressure, water (40 ml) was added to the filtrate, and the mixture was heated and stirred at 40 ° C. for 3 hours. The organic layer was separated, and the obtained organic layer was washed successively with 1N hydrochloric acid, a saturated aqueous sodium bicarbonate solution, and water, and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure to obtain a colorless liquid [H4] (45.2 g).

(Second stage)
Under a nitrogen atmosphere, a mixture of compound [H4] (30.0 g), 4-hydroxybenzoic acid methyl ester (18.9 g), potassium hydroxide (7.0 g), and methanol (300 ml) was stirred with heating under reflux for 20 hours. . The deposited salt was removed by filtration under reduced pressure, and the solvent was distilled off from the filtrate under reduced pressure. Toluene (100 ml) and water (100 ml) were added and the organic layer was separated. The obtained organic layer was washed successively with saturated aqueous sodium hydrogen carbonate and water, and the solvent was evaporated under reduced pressure. Next, methanol (60 ml), water (60 ml) and potassium hydroxide (7.6 g) were added to the residue, and the mixture was stirred for 3 hours with heating under reflux. The solvent was distilled off under reduced pressure, the residue was poured into 3N aqueous hydrochloric acid (300 ml), and the precipitated compound [H5] was filtered off under reduced pressure and purified by recrystallization (ethanol) to give colorless crystal compound [H5] (18 0.5 g) was obtained.

The NMR analysis value of compound [H5] is shown.
¹ H-NMR (CDCl ₃ ; δ ppm): 8.06 (d, 2H), 6.94 (d, 2H), 5.70 (s, 2H), 3.92 (d, 2H), 2.24 -2.08 (m, 4H), 1.97-1.84 (m, 2H), 1.59-1.50 (m, 1H).

(3rd stage)
Under a nitrogen atmosphere, thionyl chloride (245.6 g) was added to a mixture of allyl alcohol (100.0 g) and THF (248.3 g) while cooling, and the mixture was heated and stirred at 60 ° C. for 4 hours. The solvent was distilled off under reduced pressure to obtain a colorless liquid. Hydroquinone (10.0 g), potassium hydroxide (5.1 g), potassium iodide (1.0 g) and Solmix (100 ml) were added to this liquid, and the mixture was stirred for 8 hours while heating under reflux. The solvent was distilled off under reduced pressure, and toluene (200 ml) and 10% hydrochloric acid (200 ml) were added to the residue to separate the organic layer. The obtained organic layer was washed successively with saturated aqueous sodium hydrogen carbonate and water, and the solvent was evaporated under reduced pressure. The obtained residue was purified by column chromatography (silica gel, eluent: toluene-ethyl acetate mixture (volume ratio: toluene / ethyl acetate = 4/1)) to obtain a colorless liquid [H6] (5.1 g). Obtained.

The NMR analysis value of the compound [H6] is shown.
¹ H-NMR (CDCl ₃ ; δ ppm): 6.73 (s, 4H), 5.97-5.87 (m, 1H), 5.27 (d, 1H), 5.18 (d, 1H) , 4.00 (d, 2H), 3.89 (t, 2H), 1.88-1.72 (m, 4H).

(Fourth stage)
Under a nitrogen atmosphere, DCC (4.7 g) was added while cooling to a mixture of compound [H5] (5.0 g), compound [H6] (4.8 g), DMAP (0.5 g), and dichloromethane (50 ml). Stir at room temperature for 16 hours. The precipitated insoluble matter was removed by filtration under reduced pressure, water was added to the filtrate to separate the organic layer, and the obtained organic layer was washed successively with 2N hydrochloric acid and water, and dried over anhydrous magnesium sulfate. The residue obtained by distilling off the solvent under reduced pressure was subjected to column chromatography (silica gel, eluent: toluene-ethyl acetate mixture (volume ratio: toluene / ethyl acetate = 8/1)), and recrystallization (toluene-methanol mixture ( (Volume ratio: Toluene / methanol = 1/10)) to obtain colorless crystal compound [H7] (6.0 g).

The NMR analysis value of the compound [H7] is shown.
¹ H-NMR (CDCl ₃ ; δ ppm): 8.13 (d, 2H), 7.10 (d, 2H), 6.97 (d, 2H), 6.92 (d, 2H), 5.97 -5.87 (m, 1H), 5.72 (s, 2H), 5.29 (d, 1H), 5.19 (d, 1H), 4.02-3.97 (m, 4H), 3.93 (d, 2H), 2.30-2.10 (m, 5H), 1.98-1.84 (m, 5H), 1.82-1.74 (m, 2H), 1. 50-1.40 (m, 1H).

(Final stage: Synthesis of compound (1-3-21))
Under a nitrogen atmosphere, m-chloroperbenzoic acid (8.0 g) was added to a mixture of compound [H7] (6.0 g) and dichloromethane (60 ml) while cooling, and the mixture was stirred at room temperature for 16 hours. The precipitated insoluble matter was removed by filtration under reduced pressure, and the filtrate was washed successively with 10% aqueous sodium bisulfite, 3% aqueous sodium hydroxide and water, and dried over anhydrous magnesium sulfate. The residue obtained by distilling off the solvent under reduced pressure was subjected to column chromatography (silica gel, eluent: toluene-ethyl acetate mixture (volume ratio: toluene / ethyl acetate = 4/1)) and recrystallization (toluene-methanol mixture ( (Volume ratio: toluene / methanol = 1/10)) to give colorless crystal compound (1-3-11) (3.1 g).

The phase transition temperature and NMR analysis value of a compound (1-3-21) are shown.
C 86 (SmA 22 N 70)
¹ H-NMR (CDCl ₃ ; δ ppm): 8.12 (d, 2H), 7.09 (d, 2H), 6.94 (d, 2H), 6.92 (d, 2H), 3.99 (T, 2H), 3.90-3.79 (m, 2H), 3.77-3.73 (m, 1H), 3.6-3.52 (m, 2H), 3.43-3 .37 (m, 1H), 3.28-3.24 (m, 1H), 3.23-3.14 (m, 3H), 2.81 (t, 1H), 2.64-2.61 (M, 1H), 2.33-3.18 (m, 2H), 2.12-2.03 (m, 1H), 1.98-1.75 (m, 6H), 1.72-1 .52 (m, 3H), 1.37-1.27 (m, 1H), 1.22-1.13 (m, 1H).

<Synthesis of Compound (1-3-7)>
(First stage)
Under a nitrogen atmosphere, DCC (8.9 g) was cooled while cooling to a mixture of 3-cyclohexene-1-carboxylic acid (5.0 g), compound [H6] (8.8 g), DMAP (1.0 g), and dichloromethane (50 ml). ), And stirred at room temperature for 16 hours. The precipitated insoluble matter was removed by filtration under reduced pressure, water was added to the filtrate to separate the organic layer, and the obtained organic layer was washed successively with 2N hydrochloric acid and water, and dried over anhydrous magnesium sulfate. The residue obtained by distilling off the solvent under reduced pressure was purified by column chromatography (silica gel, eluent: toluene-ethyl acetate mixture (volume ratio: toluene / ethyl acetate = 8/1)) to obtain a colorless liquid [H8 ] (11.5 g) was obtained.

The NMR analysis value of the compound [H8] is shown.
¹ H-NMR (CDCl ₃ ; δ ppm): 6.97 (d, 2H), 6.87 (d, 2H), 5.93-5.87 (m, 1H), 5.73 (s, 2H) , 5.28 (d, 1H), 5.18 (d, 1H), 4.01-3.94 (m, 4H), 3.50 (t, 2H), 2.84-2.76 (m , 1H), 2.39 (d, 2H), 2.23-2.11 (m, 3H), 1.91-1.74 (m, 5H).

(Final stage: Synthesis of compound (1-3-7))
Under a nitrogen atmosphere, m-chloroperbenzoic acid (19.4 g) was added to a mixture of compound [H8] (11.0 g) and dichloromethane (110 ml) while cooling, and the mixture was stirred at room temperature for 16 hours. The precipitated insoluble matter was removed by filtration under reduced pressure, and the filtrate was washed successively with 10% aqueous sodium bisulfite, 3% aqueous sodium hydroxide and water, and dried over anhydrous magnesium sulfate. The residue obtained by distilling off the solvent under reduced pressure was purified by column chromatography (silica gel, eluent: toluene-ethyl acetate mixture (volume ratio: toluene / ethyl acetate = 4/1)) to obtain a colorless liquid (1 -3-7) (3.5 g) was obtained.

The NMR analysis value of the compound (1-3-7) is shown.
¹ H-NMR (CDCl ₃ ; δ ppm): 6.95 (d, 2H), 6.87 (d, 2H), 3.96 (t, 2H), 3.74 (d, 2H), 3.62 -3.50 (m, 2H), 3.41-3.36 (m, 1H), 3.32-3.13 (m, 3H), 2.83-2.72 (m, 2H), 2 .63-2.60 (m, 1H), 2.54-2.24 (m, 2H), 2.15-1.53 (m, 8H).

<Synthesis of Compound (1-4-24)>
(First stage)
While cooling to a mixture of 3-cyclohexene-1-carboxylic acid (10.0 g), 1-hydroxy-4-propyldicyclohexane (12.6 g), DMAP (1.9 g), and dichloromethane (100 ml) under a nitrogen atmosphere. DCC (17.2 g) was added and stirred at room temperature for 16 hours. The precipitated insoluble matter was removed by filtration under reduced pressure, water was added to the filtrate to separate the organic layer, and the obtained organic layer was washed successively with 2N hydrochloric acid and water, and dried over anhydrous magnesium sulfate. The residue obtained by distilling off the solvent under reduced pressure was purified by column chromatography (silica gel, eluent: toluene) and purified by recrystallization (toluene-methanol mixture (volume ratio: toluene / methanol = 1/5)). Compound [H9] (14.3 g) was obtained as colorless crystals.

The NMR analysis value of the compound [H9] is shown.
¹ H-NMR (CDCl ₃ ; δ ppm): 5.67 (s, 2H), 4.69-4.61 (m, 1H), 2.55-2.47 (m, 1H), 2.23 ( d, 2H), 2.12-2.06 (m, 2H), 2.02-1.94 (m, 3H), 1.80-1.63 (m, 7H), 1.35-1. 25 (m, 4H), 1.17-0.79 (m, 14H).

(Final stage: Synthesis of compound (1-4-24))
Under a nitrogen atmosphere, m-chloroperbenzoic acid (12.3 g) was added to a mixture of compound [H9] (14.0 g) and dichloromethane (140 ml) while cooling, and the mixture was stirred at room temperature for 16 hours. The precipitated insoluble matter was removed by filtration under reduced pressure, and the filtrate was washed successively with 10% aqueous sodium bisulfite, 3% aqueous sodium hydroxide and water, and dried over anhydrous magnesium sulfate. The residue obtained by evaporating the solvent under reduced pressure was purified by column chromatography (silica gel, eluent: toluene-ethyl acetate mixture (volume ratio: toluene / ethyl acetate = 8/1)) and recrystallized (toluene-methanol). Purification by a mixture (volume ratio: toluene / methanol = 1/5)) gave colorless crystal compound (1-4-24) (11.0 g).

The phase transition temperature and NMR analysis value of a compound (1-4-24) are shown.
C 127 I.I.
¹ H-NMR (CDCl ₃ ; δ ppm): 4.67-4.58 (m, 1H), 3.25-3.22 (m, 1H), 3.18-3.13 (m, 1H), 2.50-2.43 (m, 1H), 2.27-2.10 (m, 2H), 2.02-1.88 (m, 3H), 1.81-1.52 (m, 8H) ), 1.48-1.38 (m, 1H), 1.34-1.23 (m, 4H), 1.19-0.79 (m, 14H).

<Synthesis of Compound (1-2-7)>
(First stage)
Under a nitrogen atmosphere, DCC (3.6 g) was added while cooling to a mixture of compound [H2] (5.0 g), 4-cyanophenol (2.0 g), DMAP (0.4 g), and dichloromethane (100 ml). Stir at room temperature for 16 hours. The precipitated insoluble matter was removed by filtration under reduced pressure, water was added to the filtrate to separate the organic layer, and the obtained organic layer was washed successively with 2N hydrochloric acid and water, and dried over anhydrous magnesium sulfate. The residue obtained by distilling off the solvent under reduced pressure was purified by column chromatography (silica gel, eluent: toluene-ethyl acetate mixture (volume ratio: toluene / ethyl acetate = 8/1)) and recrystallized (toluene-methanol). Purification by a mixture (volume ratio: toluene / methanol = 1/10)) gave colorless crystal compound [H10] (5.2 g).

The NMR analysis value of compound [H10] is shown.
¹ H-NMR (CDCl ₃ ; δ ppm): 8.12 (d, 2H), 7.74 (d, 2H), 7.35 (d, 2H), 6.98 (d, 2H), 5.67 (S, 2H), 4.09 (t, 2H), 3.50 (t, 2H), 3.36-3.29 (m, 2H), 2.15-2.03 (m, 3H), 1.97-1.70 (m, 7H), 1.33-1.24 (m, 1H).

(Final Stage: Synthesis of Compound (1-2-7)>
Under a nitrogen atmosphere, m-chloroperbenzoic acid (3.6 g) was added to a mixture of compound [H10] (5.0 g) and dichloromethane (50 ml) while cooling, and the mixture was stirred at room temperature for 16 hours. The precipitated insoluble matter was removed by filtration under reduced pressure, and the filtrate was washed successively with 10% aqueous sodium bisulfite, 3% aqueous sodium hydroxide and water, and dried over anhydrous magnesium sulfate. The residue obtained by evaporating the solvent under reduced pressure was purified by column chromatography (silica gel, eluent: toluene-ethyl acetate mixture (volume ratio: toluene / ethyl acetate = 8/1)) and recrystallized (toluene-methanol). Purification by a mixture (volume ratio: toluene / methanol = 1/5)) gave colorless compound (1-2-7) (3.7 g).

The phase transition temperature and NMR analysis value of a compound (1-2-7) are shown.
C 61 I.I.
¹ H-NMR (CDCl ₃ ; δ ppm): 8.13 (d, 2H), 7.73 (d, 2H), 7.35 (d, 2H), 6.98 (d, 2H), 4.08 (T, 2H), 3.46 (t, 2H), 3.29-3.14 (m, 4H), 2.19-2.12 (m, 1H), 2.10-1.97 (m , 1H), 1.95-1.70 (m, 6H), 1.60-1.4 (m, 2H), 1.20-0.95 (m, 1H).

<Synthesis of Compound (1-1-3)>
(First stage)
Under a nitrogen atmosphere, a mixture of hydroquinone (52.9 g), compound [H1] (59.3 g), sodium hydroxide (19.2 g), and DMF (300 ml) was stirred with heating at 80 ° C. for 6 hours. The precipitated salt was removed by vacuum filtration. Toluene (500 ml) and water (500 ml) were added to the filtrate to separate the organic layer. The obtained organic layer was washed successively with saturated aqueous sodium hydrogen carbonate and water, and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, and the resulting residue was purified by column chromatography (silica gel, eluent: toluene-ethyl acetate mixture (volume ratio: toluene / ethyl acetate = 4/1)) to obtain a colorless liquid [ H11] (39.9 g) was obtained.

The NMR analysis value of compound [H11] is shown.
¹ H-NMR (CDCl ₃ ; δ ppm): 6.80-6.72 (m, 4H), 5.66 (s, 2H), 5.27 (s, 1H), 3.91 (t, 2H) , 3.50 (t, 2H), 3.38-3.29 (m, 2H), 2.16-2.02 (m, 3H), 1.97-1.68 (m, 7H), 1 .32-1.21 (m, 1H).

(Second stage)
Under a nitrogen atmosphere, DCC (17.8 g) was added while cooling to a mixture of compound [H2] (25.0 g), compound [H11] (20.2 g), DMAP (2.0 g) and dichloromethane (250 ml). Stir at room temperature for 16 hours. The precipitated insoluble matter was removed by filtration under reduced pressure, water was added to the filtrate to separate the organic layer, and the obtained organic layer was washed successively with 2N hydrochloric acid and water, and dried over anhydrous magnesium sulfate. The residue obtained by distilling off the solvent under reduced pressure was subjected to column chromatography (silica gel, eluent: toluene-ethyl acetate mixture (volume ratio: toluene / ethyl acetate = 8/1)), and recrystallization (toluene-methanol mixture ( (Volume ratio: toluene / methanol = 1/10)) to obtain colorless crystals of compound [H12] (35.4 g).

The NMR analysis value of the compound [H12] is shown.
¹ H-NMR (CDCl ₃ ; δ ppm): 8.12 (d, 2H), 7.09 (d, 2H), 6.96 (d, 2H), 6.91 (d, 2H), 5.67 (S, 2H), 4.08 (t, 2H), 3.99 (t, 2H), 3.53-3.47 (m, 4H), 3.36-3.27 (m, 4H), 2.17-2.02 (m, 6H), 1.97-1.70 (m, 14H), 1.34-1.23 (m, 2H).

(Final stage: Synthesis of compound (1-1-3))
Under a nitrogen atmosphere, m-chloroperbenzoic acid (31.1 g) was added to a mixture of compound [H12] (30.0 g) and dichloromethane (300 ml) while cooling, and the mixture was stirred at room temperature for 16 hours. The precipitated insoluble matter was removed by filtration under reduced pressure, and the filtrate was washed successively with 10% aqueous sodium bisulfite, 3% aqueous sodium hydroxide and water, and dried over anhydrous magnesium sulfate. The residue obtained by distilling off the solvent under reduced pressure was subjected to column chromatography (silica gel, eluent: toluene-ethyl acetate mixture (volume ratio: toluene / ethyl acetate = 4/1)) and recrystallization (toluene-methanol mixture ( (Volume ratio: toluene / methanol = 1/10)) to give colorless crystal compound (1-1-3) (18.7 g).

The phase transition temperature and NMR analysis value of a compound (1-1-3) are shown.
C46 (N-6) I.I.
¹ H-NMR (CDCl ₃ ; δ ppm): 8.13 (d, 2H), 7.89 (d, 2H), 6.96 (d, 2H), 6.91 (d, 2H), 4.07 (T, 2H), 3.98 (t, 2H), 3.49-3.43 (m, 4H), 3.28-3.13 (m, 8H), 2.20-1.70 (m , 15H), 1.62-1.40 (m, 5H), 1.20-0.97 (m, 2H).

<Synthesis of Compound (1-2-6)>
(First stage)
Under a nitrogen atmosphere, DCC (14.2 g) was added while cooling to a mixture of compound [H2] (20.0 g), 4-methoxyphenol (8.2 g), DMAP (1.6 g), and dichloromethane (200 ml). Stir at room temperature for 16 hours. The precipitated insoluble matter was removed by filtration under reduced pressure, water was added to the filtrate to separate the organic layer, and the obtained organic layer was washed successively with 2N hydrochloric acid and water, and dried over anhydrous magnesium sulfate. The residue obtained by distilling off the solvent under reduced pressure was purified by column chromatography (silica gel, eluent: toluene-ethyl acetate mixture (volume ratio: toluene / ethyl acetate = 8/1)) and recrystallized (toluene-methanol). Purification by a mixture (volume ratio: toluene / methanol = 1/10)) gave colorless crystal compound [H13] (23.1 g).

The NMR analysis value of the compound [H13] is shown.
¹ H-NMR (CDCl ₃ ; δ ppm): 8.13 (d, 2H), 7.11 (d, 2H), 6.97 (d, 2H), 6.94 (d, 2H), 5.67 (S, 2H), 4.08 (t, 2H), 3.82 (s, 3H), 3.50 (t, 2H), 3.36-3.29 (m, 2H), 2.18- 2.07 (m, 3H), 1.96-1.71 (m, 7H), 1.34-1.25 (m, 1H).

(Final Stage: Synthesis of Compound (1-2-6)>
Under a nitrogen atmosphere, m-chloroperbenzoic acid (16.2 g) was added to a mixture of compound [H13] (22.7 g) and dichloromethane (230 ml) while cooling, and the mixture was stirred at room temperature for 16 hours. The precipitated insoluble matter was removed by filtration under reduced pressure, and the filtrate was washed successively with 10% aqueous sodium bisulfite, 3% aqueous sodium hydroxide and water, and dried over anhydrous magnesium sulfate. The residue obtained by evaporating the solvent under reduced pressure was purified by column chromatography (silica gel, eluent: toluene-ethyl acetate mixture (volume ratio: toluene / ethyl acetate = 8/1)) and recrystallized (toluene-methanol). Purification by a mixture (volume ratio: toluene / methanol = 1/5)) gave colorless compound (1-2-6) (17.9 g).

The phase transition temperature and NMR analysis value of a compound (1-2-6) are shown.
C 61 I.I.
¹ H-NMR (CDCl ₃ ; δ ppm): 8.13 (d, 2H), 7.11 (d, 2H), 6.96 (d, 2H), 6.93 (d, 2H), 4.07 (T, 2H), 3.82 (s, 2H), 3.45 (t, 2H), 3.28-3.14 (m, 4H), 2.18-1.97 (m, 2H), 1.92-1.72 (m, 6H), 1.58-1.42 (m, 3H), 1.22-0.94 (m, 1H).

<Synthesis of Compound (1-1-45)>
(First stage)
Under a nitrogen atmosphere, DCC (7.1 g) was added while cooling to a mixture of compound [H2] (10.0 g), methoxyhydroquinone (2.3 g), DMAP (0.8 g) and dichloromethane (100 ml) at room temperature. Stir for 16 hours. The precipitated insoluble matter was removed by filtration under reduced pressure, water was added to the filtrate to separate the organic layer, and the obtained organic layer was washed successively with 2N hydrochloric acid and water, and dried over anhydrous magnesium sulfate. The residue obtained by distilling off the solvent under reduced pressure was purified by column chromatography (silica gel, eluent: toluene-ethyl acetate mixture (volume ratio: toluene / ethyl acetate = 8/1)) and recrystallized (toluene-methanol). Purification by a mixture (volume ratio: toluene / methanol = 1/10)) gave colorless crystal compound [H14] (7.8 g).

The NMR analysis value of compound [H14] is shown.
¹ H-NMR (CDCl ₃ ; δ ppm): 8.15 (t, 4H), 7.17 (d, 1H), 7.01-6.96 (m, 4H), 6.88 (d, 1H) , 6.86-6.82 (m, 1H), 5.68 (s, 4H), 4.12-4.07 (m, 4H), 3.81 (s, 3H), 3.51 (t , 4H), 3.37-3.29 (m, 4H), 2.16-2.03 (m, 6H), 1.96-1.86 (m, 6H), 1.86-1.70. (M, 8H), 1.34-1.24 (m, 2H).

(Final Stage: Synthesis of Compound (1-1-45)>
Under a nitrogen atmosphere, m-chloroperbenzoic acid (6.4 g) was added to a mixture of compound [H14] (7.8 g) and dichloromethane (80 ml) while cooling, and the mixture was stirred at room temperature for 16 hours. The precipitated insoluble matter was removed by filtration under reduced pressure, and the filtrate was washed successively with 10% aqueous sodium bisulfite, 3% aqueous sodium hydroxide and water, and dried over anhydrous magnesium sulfate. The residue obtained by distilling off the solvent under reduced pressure was purified by column chromatography (silica gel, eluent: toluene-ethyl acetate mixture (volume ratio: toluene / ethyl acetate = 4/1)) and dried under reduced pressure. An oil (1-1-45) (5.2 g) was obtained. This compound was in a liquid crystal state at room temperature.

The phase transition temperature and NMR analysis value of a compound (1-1-45) are shown.
N 55 I.
¹ H-NMR (CDCl ₃ ; δ ppm): 8.15 (t, 4H), 7.17 (d, 1H), 7.00-6.95 (m, 4H), 6.89 (d, 1H) 6.86-6.82 (m, 1H), 4.11-4.05 (m, 4H), 3.80 (s, 3H), 3.46 (t, 4H), 3.29-3 3.12 (m, 8H), 2.19-2.2.12 (m, 2H), 2.11-1.96 (m, 2H), 1.94-1.70 (m, 12H) 1.61-1.40 (m, 4H), 1.24-1.10 (m, 1H), 1.06-0.95 (m, 1H).

<Synthesis of Compound (1-1-46)>
(First stage)
DCC (7.1 g) while cooling to a mixture of compound [H2] (10.0 g), 4,4′-dihydroxybiphenyl (3.1 g), DMAP (0.8 g), dichloromethane (100 ml) under a nitrogen atmosphere. And stirred at room temperature for 16 hours. The precipitated insoluble matter was removed by filtration under reduced pressure, water was added to the filtrate to separate the organic layer, and the obtained organic layer was washed successively with 2N hydrochloric acid and water, and dried over anhydrous magnesium sulfate. The residue obtained by distilling off the solvent under reduced pressure was purified by column chromatography (silica gel, eluent: toluene-ethyl acetate mixture (volume ratio: toluene / ethyl acetate = 8/1)) and recrystallized with ethyl acetate. To obtain colorless compound [H15] (8.1 g).

The NMR analysis value of the compound [H15] is shown.
¹ H-NMR (CDCl ₃ ; δ ppm): 8.17 (d, 4H), 7.63 (d, 4H), 7.29 (d, 4H), 6.99 (d, 4H), 5.68 (S, 4H), 4.09 (t, 4H), 3.51 (t, 4H), 3.37-3.29 (m, 4H), 2.16-2.03 (m, 6H), 1.97-1.86 (m, 6H), 1.86-1.70 (m, 8H), 1.34-1.24 (m, 2H).

(Final Stage: Synthesis of Compound (1-1-46)>
Under a nitrogen atmosphere, m-chloroperbenzoic acid (6.1 g) was added to a mixture of compound [H15] (7.9 g) and dichloromethane (80 ml) while cooling, and the mixture was stirred at room temperature for 16 hours. The precipitated insoluble matter was removed by filtration under reduced pressure, and the filtrate was washed successively with 10% aqueous sodium bisulfite, 3% aqueous sodium hydroxide and water, and dried over anhydrous magnesium sulfate. The residue obtained by distilling off the solvent under reduced pressure was purified by column chromatography (silica gel, eluent: toluene-ethyl acetate mixture (volume ratio: toluene / ethyl acetate = 2/1)) and dried under reduced pressure. A colorless liquid compound (1-1-45) (4.6 g) was obtained.

The phase transition temperature and NMR analysis value of a compound (1-1-46) are shown.
C 117 N 250 <I.
¹ H-NMR (CDCl ₃ ; δ ppm): 8.17 (d, 4H), 7.63 (d, 4H), 7.28 (d, 4H), 6.99 (d, 4H), 4.08 (T, 4H), 3.29-3.13 (m, 8H), 2.20-2.13 (m, 2H), 2.11-1.97 (m, 2H), 1.95-1 .64 (m, 12H), 1.62-1.40 (m, 4H), 1.21-1.10 (m, 1H), 1.06-0.96 (m, 1H).

The compound which is components other than a compound (1) used in the Example of the following polymeric liquid crystal composition is shown. These compounds can be synthesized by combining organic synthetic chemistry techniques. Methods for introducing the desired end groups, rings and linking groups into the starting material are described by Houben-Wyle, Methods of Organic Chemistry, Georg Thieme Verlag, Stuttgart, Organic Syntheses, John Wily & Sons. , Inc.), Organic Reactions (John Wily & Sons Inc.), Comprehensive Organic Synthesis (Pergamon Press), New Experimental Chemistry Course (Maruzen), etc. ing.

  A specific method for producing the above compound will be described. The compound (M1-1-1) and the compound (M1-1-3) are described in JP-A-2005-60373. The compound (M1-1-2) is described in JP-A-2005-97281. The compound (M1-7-1) is described in Polymer, 34 (8), 1736-1740 (1993). Compound (M1-19-1) and compound (M1-19-2) are described in Macromolecules, 26, 1244-1247 (1993). The compound (M2-13-1) is described in JP-A-2005-320317. The compound (6-8-1) is described in JP-A No. 2005-263778. Compound (M1-7-2) can be synthesized in the same manner as compound (M1-1-1) by changing 9-methyl-2,7-dihydroxyfluorene to methylhydroquinone. The compound (M1-7-3) is described in Makromol. Chem., 190, 2255-2268 (1989).

Compound (1-1-20) / polymerization initiator CPI-110P (manufactured by San Apro) was mixed at a weight ratio of 100 / 0.02, and dissolved in cyclopentanone to obtain a solution having a compound concentration of 20% by weight. Prepared. This solution was taken in an aluminum pan and placed on a hot plate heated to 80 ° C. for 30 minutes to evaporate the solvent.
Next, using a photochemical reaction calorimeter PDC121 (Seiko Instruments Inc.), a sample on an aluminum pan was irradiated with ultraviolet light (365 nm, 15 mW / cm ² ) at 25 ° C. under a flow of dry air. To the peak top was observed.

[Comparative Example 1]
Except that the compound (1-1-20) was replaced with the compound (M1-7-2), measurement was carried out in the same manner as in Example 10. As a result, an exothermic peak slowly reaching the peak top was confirmed.

  Compound (1-2-14) and compound (M1-19-1) are mixed at a weight ratio of 70/30, and this is mixed with a mixed solvent of PGMEA / MMP = 9/1 (weight ratio) to obtain a compound. A composition having a concentration of 30% by weight was prepared. When this composition was allowed to stand at room temperature, no crystal deposition or the like was observed for 3 days or more. PGMEA is an abbreviation for propylene glycol monoethyl ether acetate, and MMP is an abbreviation for methyl 3-methoxypropionate.

[Comparative Example 2]
A composition was prepared by the method described in Example 11 except that the compound (1-2-14) was replaced with the compound (M1-7-2). When this composition was allowed to stand at room temperature, precipitation of crystals was observed in 1 hour.

Compound (1-1-20) / Compound (1-2-7) was mixed at a weight ratio of 80/20, and this was mixed with n-butyl acetate to prepare a composition having a compound concentration of 20% by weight. did. A silicone-based nonionic surfactant BYK-333 (manufactured by Big Chemie Japan Co., Ltd.) having a weight ratio of 0.001 and a polymerization initiator CPI-110P having a weight ratio of 0.02 were added to the composition. This solution was applied to a glass substrate having a rubbed polyimide alignment film by a spin coater. The glass substrate was placed on a hot plate heated to 70 ° C. for 120 seconds to evaporate the solvent.
Next, polymerization was performed by irradiation with light having an intensity of 30 mW / cm ² (center wavelength: 365 nm) for 30 seconds using an ultrahigh pressure mercury lamp of 250 W at room temperature in the atmosphere. The obtained thin film had a homogeneous orientation fixed, and exhibited A-plate optical characteristics.

  Compound (1-1-20) / Compound (M1-19-1) / Compound (M1-1-3) was mixed at a weight ratio of 60/30/10, and this was mixed with PGMEA / cyclopentanone = 1/1 ( A composition having a compound concentration of 20% by weight was prepared. A fluorine-based nonionic surfactant FTX-218 (manufactured by Neos Co., Ltd.) having a weight ratio of 0.002 and a polymerization initiator CPI-110P having a weight ratio of 0.02 were added to the composition. Using this solution, a thin film was prepared according to Example 12, and exhibited A-plate optical characteristics.

  Compound (1-3-21) / Compound (M1-19-2) was mixed at a weight ratio of 70/30, and this was mixed with PGMEA / MMP = 1/1 (volume ratio) to obtain a compound concentration of 20 A weight percent composition was prepared. Hydrocarbon-based nonionic surfactant Polyflow No. 0.002 having a weight ratio of 0.002 to this composition. 75 (manufactured by Kyoeisha Chemical Co., Ltd.) and a weight ratio of 0.02 polymerization initiator CPI-110P were added. Using this solution, a thin film was prepared according to Example 12, and exhibited A-plate optical characteristics.

  Compound (1-1-20) / Compound (M1-7-1) / Compound (M1-1-3) was mixed at a weight ratio of 80/10/10, and this was mixed with cyclopentanone to obtain a compound. A composition having a concentration of 20% by weight was prepared. To this composition, a fluorine-based nonionic surfactant FTX-218 having a weight ratio of 0.002 and a polymerization initiator DTS-102 (manufactured by Midori Chemical) having a weight ratio of 0.02 were added. Using this solution, a thin film was prepared according to Example 12, and exhibited A-plate optical characteristics.

Compound (1-3-21) / Compound (M1-19-1) / Compound (M2-13-1) were mixed at a weight ratio of 35/30/35, and this was mixed with PGMEA / MMP = 9/1 (volume ratio). ) To prepare a composition having a compound concentration of 20% by weight. A solution obtained by adding a polymerization initiator CPI-110P having a weight ratio of 0.02 to the composition was applied to a glass substrate with a spin coater to form a thin film. The glass substrate was placed on a hot plate heated to 70 ° C. for 120 seconds to evaporate the solvent.
Next, polymerization was performed by irradiation with light having an intensity of 30 mW / cm ² (center wavelength: 365 nm) for 30 seconds using an ultrahigh pressure mercury lamp of 250 W at room temperature in the atmosphere. The obtained thin film had a homogeneous orientation fixed and exhibited C plate optical characteristics.

  Compound (1-1-20) / Compound (1-3-21) / Compound (M1-1-1) / Compound (6-8-1) were mixed at a weight ratio of 60/15/15/10. Was dissolved in a mixed solvent of PGMEA / cyclopentanone = 3/7 (volume ratio) to prepare a composition having a compound concentration of 20% by weight. A fluorine-based nonionic surfactant FTX-218 having a weight ratio of 0.002 and a polymerization initiator CPI-110P having a weight ratio of 0.02 were added to the composition. When this solution was used to form a thin film according to Example 12, it exhibited negative C plate optical characteristics.

  Compound (1-1-20) / Compound (M1-19-1) / Compound (M1-1-2) was mixed at a weight ratio of 30/40/30, and this was mixed with methyl ethyl ketone to obtain a compound concentration of A 20% by weight composition was prepared. A fluorine-based nonionic surfactant FTX-218 having a weight ratio of 0.002 and a polymerization initiator CPI-110P having a weight ratio of 0.02 were added to the composition. Using this solution, a thin film was prepared according to Example 12, and showed visible light selective reflection.

  Compound (1-4-24) / Compound (M1-1-1) / Compound (M2-13-1) was mixed at a weight ratio of 10/75/15, and this was dissolved in toluene to give a compound concentration of A 20% by weight composition was prepared. A polymerization initiator DTS-102 having a weight ratio of 0.02 was added to the composition. Using this solution, a thin film was prepared according to Example 12, and showed O-plate optical properties.

  Compound (1-1-46) / Compound (1-1-3) / Compound (M1-7-3) / Compound (6-8-1) were mixed at a weight ratio of 40/20/30/10. Was dissolved in a mixed solvent of PGMEA / cyclopentanone = 3/7 (volume ratio) to prepare a composition having a compound concentration of 20% by weight. A polymerization initiator Irgacure 250 having a weight ratio of 0.02, a polymerization initiator Irgacure 184 having a weight ratio of 0.02, and a photosensitizer Z-4 having a weight ratio of 0.01 were added to the composition. When this solution was used to form a thin film according to Example 12, it exhibited negative C plate optical characteristics.

  The compound of the present invention can be used as a polymerizable liquid crystal compound and can be used as a component of a polymerizable liquid crystal composition. The polymer of the present invention can be used for, for example, a retardation plate, a polarizing element, a selective reflection film, a brightness enhancement film, a viewing angle compensation film, and the like, which are constituent elements of a liquid crystal display element.

Claims (17)

Polymerizable liquid crystal compound represented by formula (1):

Wherein A ¹ and A ² are independently 1,4-cyclohexylene or 1,4-phenylene;
In this 1,4-phenylene, any hydrogen may be replaced by fluorine or methyl; Z ¹ is a single bond, —COO— or —OCO; m is an integer of 1 or 2; Any ^two of ring A ² may be the same or different, and any two of Z ¹ may be the same or different; P ¹ is A polymerizable group represented by formula (2-1); Q ¹ is —CH ₂ O—, —CH ₂ O (CH ₂ ) rO—, —COO— or —COO (CH ₂ ) rO—; , R is an integer of 1 to 17; P ² is a polymerizable group represented by the formula (2-1); Q ² is —OCH ₂ — , —O (CH ₂ ) sOCH ₂ —, —OCO. - or _-O (CH 2) a sOCO-, s is an integer of 1 to 17.

Polymerizable liquid crystal containing at least one polymerizable liquid crystal compound represented by formula (1) and at least one compound selected from the group of polymerizable liquid crystal compounds represented by formula (M1) and formula (M2) Composition:

Where A ¹ and A ² are independently 1,4-cyclohexylene or 1,4-phenylene

In this 1,4-phenylene, any hydrogen may be replaced by fluorine or methyl; Z ¹ is a single bond, —COO— or —OCO—; m is an integer of 1 or 2 When m is 2, any ^two of ring A ² may be the same or different and any two of Z ¹ may be the same or different P ¹ is a polymerizable group represented by formula (2-1); Q ¹ is —CH ₂ O—, —CH ₂ O (CH ₂ ) rO—, —COO— or —COO (CH ₂ ); rO—, r is an integer of 1 to 17; P ² is a polymerizable group represented by the formula (2-1); Q ² is —OCH ₂ — , —O (CH ₂ ) sOCH _2. -, -OCO- or _-O (CH 2) a sOCO-, s is an 1 to 17 integer:

Where A ³ and A ⁴ are independently 1,4-cyclohexylene, 1,4-phenylene, naphthalene-2,6-diyl, fluorene-2,7-diyl or 1,3-dioxane-2, In this 1,4-phenylene and fluorene-2,7-diyl, any hydrogen may be replaced by fluorine or chlorine, and any hydrogen may be cyano, methyl, ethyl, methoxy, hydroxy , Formyl, acetoxy, acetyl, trifluoroacetyl, difluoromethyl, or trifluoromethyl; Z ² is independently a single bond, —O—, —COO—, —OCO—, —CH═CH _{-COO -, - OCO-CH =} CH -, - OCO-CH 2 CH 2 -, - CH 2 CH 2 -COO -, - CH≡CH-COO-, _{OCO-CH≡CH -, - CH 2} O -, - OCH 2 -, - CF 2 O -, - OCF 2 -, - CONH -, - NHCO -, - (CH 2) 4 -, - CH 2 CH 2 _{-, - CF 2 CF 2 -} , - CH = CH -, - CF = CF-, or a -C≡C-; n is an integer from 0 to 5; when n is 2 or more, the ring a Any two of ⁴ may be the same or different, any ^two of Z ² may be the same or different; Q ³ and Q ⁴ are independently An alkylene having 1 to 20 carbon atoms, and any hydrogen in the alkylene may be replaced by fluorine, and any —CH ₂ — may be —O—, —COO—, —OCO—, —CH═CH—; Or -C≡C-; R may be fluorine, cyano, trifluoromethyl, Either one of ^{P 3} and ^{P 4} are each independently formula (2-2) to (2-4); trifluoromethoxy, alkyl of 1 to 20 carbons or alkoxy having 1 to 20 carbon atoms In the formula (2-2) to formula (2-4), R ^a is independently hydrogen, halogen, or alkyl having 1 to 5 carbon atoms. In formula (1), A ¹ and A ² are each independently 1,4-cyclohexylene or 1,4-phenylene, and in this 1,4-phenylene, any hydrogen may be replaced by fluorine or methyl. Well; Z ¹ is a single bond, —COO— or —OCO—; m is an integer of 1 to 2; P ² is a polymerizable group represented by formula (2-1); and Q ¹ is _{-CH 2 O -, - CH 2} O (CH 2) rO -, - COO- or -COO _(CH 2) a RO-, r is an 1-17 integer; ^{Q 2} is -OCH ₂ -, _{-O (CH 2) sCH 2 O} -, - OCO- or _-O (CH _{2) sOCH} 2 - a and, s is an 1-17 integer;
In Formula (M1) and Formula (M2), A ³ and A ⁴ are independently 1,4-cyclohexylene or 1,4-phenylene, and any one or two of the 1,4-phenylene Hydrogen may be replaced by fluorine, methyl or trifluoromethyl; Z ² is independently a single bond, —O—, —COO—, or —OCO—; n is an integer from 1 to 3; Q ³ and Q ⁴ are each independently alkylene having 1 to 14 carbons, and any hydrogen in the alkylene may be replaced by fluorine, and any —CH ₂ — may be —O—, —COO— or -OCO- may be substituted; R ^a in formula (2-2) to formula (2-4) is independently hydrogen, methyl or ethyl:
Based on the total amount of the compound selected from the group consisting of the polymerizable liquid crystal compound represented by formula (1) and the polymerizable liquid crystal compound represented by formula (M1) and formula (M2), the formula (1) The ratio of the polymerizable liquid crystal compound represented by the formula is 5 to 95% by weight, and the ratio of the compound selected from the group of polymerizable liquid crystal compounds represented by the formulas (M1) and (M2) is 5 to 95% by weight. The polymerizable liquid crystal composition according to claim 2, wherein In formula (1), A ¹ and A ² are independently 1,4-cyclohexylene or 1,4-phenylene, and any one or two hydrogens in the 1,4-phenylene are fluorine or methyl Z ¹ is a single bond, —COO— or —OCO—; m is 1 or 2; P ² is a polymerizable group represented by formula (2-1); Q ¹ is _{-CH 2 O -, - CH 2} O (CH 2) rO -, - COO- or -COO _(CH 2) a RO-, r is an 1-17 integer; ^{Q 2} is -OCH _{2 -, -O (CH 2)} sOCH 2 -, -OCO- or _-O (CH 2) a sOCO-, s is an 1 to 17 integer:
In Formula (M1) and Formula (M2), A ³ and A ⁴ are independently 1,4-cyclohexylene or 1,4-phenylene, and any one or two of the 1,4-phenylene Hydrogen may be replaced by fluorine, methyl or trifluoromethyl; Z ² is independently a single bond, —O—, —COO— or —OCO—; n is 1 or 2; Q ³ and Q ⁴ is independently alkylene having 1 to 14 carbons, and any hydrogen in the alkylene may be replaced by fluorine, and any —CH ₂ — may be —O—, —COO— or —OCO—. R ^a in formula (2-2) to formula (2-4) is independently hydrogen, methyl or ethyl:
Based on the total amount of the compound selected from the group consisting of the polymerizable liquid crystal compound represented by formula (1) and the polymerizable liquid crystal compound represented by formula (M1) and formula (M2), the formula (1) The ratio of the polymerizable liquid crystal compound represented by the formula is 10 to 90 wt%, and the ratio of the compound selected from the group of the polymerizable liquid crystal compounds represented by the formula (M1) and the formula (M2) is 10 to 90 wt%. The polymerizable liquid crystal composition according to claim 2, wherein   Expressed by the formula (1) on the basis of the total amount of the compound selected from the group consisting of the polymerizable liquid crystal compound represented by the formula (1) and the polymerizable liquid crystal compound represented by the formula (M1) and the formula (M2). The ratio of the compound to be selected is 30 to 80% by weight, and the ratio of the compound selected from the group of polymerizable liquid crystal compounds represented by the formulas (M1) and (M2) is 20 to 70% by weight. The polymerizable liquid crystal composition according to any one of 2 to 4.   Expressed by the formula (1) on the basis of the total amount of the compound selected from the group consisting of the polymerizable liquid crystal compound represented by the formula (1) and the polymerizable liquid crystal compound represented by the formula (M1) and the formula (M2). The proportion of the polymerizable liquid crystal compound is 40 to 70% by weight, and the proportion of the compound selected from the group of polymerizable liquid crystal compounds represented by formula (M1) and formula (M2) is 30 to 60% by weight. The polymerizable liquid crystal composition according to any one of claims 2 to 4.   The polymerizable liquid crystal composition according to claim 2, further containing another polymerizable compound.   The polymerizable liquid crystal composition according to claim 2, further comprising a polymerizable optically active compound.   The polymerizable liquid crystal composition according to claim 2, further comprising a non-polymerizable liquid crystal compound.   The polymerizable liquid crystal composition according to claim 2, further comprising a non-polymerizable optically active compound.   A film having optical anisotropy, comprising a polymer obtained by polymerizing at least one of the compounds according to claim 1.   A film having optical anisotropy obtained by polymerizing the polymerizable liquid crystal composition according to claim 2.   The film having optical anisotropy according to claim 11 or 12, which has the optical properties of an A plate.   The film having optical anisotropy according to claim 11 or 12, having optical properties of a C plate.   The film having optical anisotropy according to claim 11 or 12, having optical characteristics of a negative C plate.   The film having optical anisotropy according to claim 11 or 12, having optical characteristics of an O plate.   The liquid crystal display element containing the film which has the optical anisotropy of any one of Claims 11-16.